Reaction of Aminocarbene Complexes of Chromium with Alkynes. 5

Organometallics 1995, 14, 2760-2774

2760

Reaction of Aminocarbene Complexes of Chromium with Alkynes. 5. Influence of the Ring Size on the Product Distribution. Formation of Pyrroles from Pyrrolidine and Its Derivative-Substituted Carbene Complexes Andrke Parlier, Michele Rudler, Henri Rudler," Regis Goumont, Jean-Claude Daran, and Jacqueline Vaissermann Laboratoire de Chimie Organique, URA 408, and Laboratoire de Chimie des Mt!taux de Transition URA 608, Universitt! Pierre et Marie Curie, 4 place Jussieu, 75252 Paris Cedex 5, France Received July 22, 1994@

A series of aminocarbene complexes of chromium derived from piperidine (11, hexa- and heptamethyleneimine (4) and (8),pyrrolidine (13a-d, R1= Me, H, Ph, thienyl), perhydroindole (21), thiazolidine (24a,b, R1 = Me, Ph), pyrroline (30a,b), and azetidine (33a-e and 36) have been synthesized and subjected to alkyne insertion reactions. Aminocarbene complex 24a-E has been fully characterized by X-ray structure anal sis. Crystal data for 24a-E: CloH905NSCr,monoclinic, space group P21/n, a = 8.3011(9) b = 11.949(1) c = 13.101(2) A, p = 95.74(1)", v = 1293(1)A3, dcalcd= 1.41 g 6111-3, z = 4. Whereas complex 1 reacted with diphenylacetylene to give first the ylide complex 2, the thermolysis of which led t o the bridgehead lactam 3, complexes 4, and 8 gave directly the expected bridgehead lactams 6 and 11. The structure of 3 has been determined by X-ray diffraction. Crystal data for 3: C27H250N, monoclinic, space group P21/c, a = 10.080(4) b = 11.727(3) A, c = 18.014(6) p = 102.40(3)", v = 2080(14) A3, dcalcd = 1.21 g ~ m - z~ =, 4. In contrast to 1, 4, and 8, all of the new carbene complexes derived from five-membered cycloamines except 24b gave pyrrole derivatives a s the result of the alkyne/CO insertion followed by migration of a n alkyl chain from nitrogen to the carbon atom of the inserted carbonyl group and loss of its oxygen atom. The structures of 14a, the Cr(C0)3 complex of 15a, and 22 could be unambiguously established by X-ray crystallography. Crystal data for 15: C24H2103NCr, triclinic, space group P1, a = 6.918(1) A, b = 10.057(1) c = 15.193(2) a = 72.410(9)", p = 84.99(1)", y = 84.66(3)", V = l O O l ( 3 ) A3, dcalcd = 1.40 g ~ m - z~ =, 2. For 22: C N H ~ ~ N , b = 10.682(2) c = 15.428(3) p= monoclinic, space group P2Jn, a = 11.119(3) 102.23(2)",V = 1791(7)A3, dcalcd= 1.21 g ~ m - Z~=, 4. Besides these pyrroles, the expected bridgehead lactams 17a-d were isolated from 13a-d together with the lactone complex 18 in the case of 13b. Crystal data for 18: C19H120&r, orthorhombic, space group Pc2l/b, a = 10.356(1) b = 12.366(5) A, C = 12.529(2) v = 1604.4(8) A3, dcalcd = 1.54 g z = 4. However, 24b gave a s the major insertion product the aminofuran 26, and pyrroline-derived carbene complexes 30a,b gave lactams 32a,b and trace amounts of pyrroles 31a,b. Only trace amounts of pyrroles were detected starting from carbene complexes derived from azetidine (33a-e) and 36, which gave mainly the lactams 35a,d and 37. Mechanisms for these new transformations of aminocarbene complexes of chromium based on the behavior of the Stevens-type acyl-stabilized N-ylides will be suggested.

g

A,

A,

A,

A,

A,

A,

A,

A,

A,

A,

Introduction The isolation of N-ylide complexes during the interaction of alkynes with aminocarbene complexes of chromium and their thermal transformation into lactams upon migration of alkyl groups from nitrogen t o carbon atoms brought t o light large analogies between these zwitterionic species and those discovered by Stevens, especially regarding the manner by which they rearrange thermally. In previous papers,lBz we described mainly products arising from the migration of the substituents from nitrogen t o the a and y carbons of the intermediate N-ylide complexes. The present pubAbstract published in Advance ACS Abstracts, May 1, 1995. (1)Chelain, E.;Goumont, R.; Hamon, L.; Parlier, A,; Rudler, M.; Rudler, H.; Daran, J. C.; Vaissermann, J. J . Am. Chem. SOC.1992, @

114, 8088. (2) Chelain, E.; Parlier, A,; Audouin, M.; Rudler, H.; Daran, J. C.;

Vaissermann, J. J. Am. Chem. SOC.1993,115, 10568.

lication deals with the formation of pyrroles due to the migration of alkyl groups from nitrogen t o the central carbon atom of the ketene function and the formation of aminofurans due to the cleavage of a carbon-nitrogen bond followed by the formation of a carbon-oxygen

bond.

Results Synthesis of the Aminocarbene Complexes. Complexes 1, 13a,c,d, 24a,b, 30a,b, 33b-d, and 36 were obtained by aminolysis of the corresponding ethoxy carbene complexes with the proper ~ y c l o a m i n e ;com~,~ plexes 4, 8, 13b, 21,33a, and 33e were prepared from the formyl derivatives of the corresponding cycloamines (3) Moser, E.; Fischer, E. 0. J . Organomet. Chem. 1968,15, 147.

Q276-7333l95l2314-276Q$Q9.QQ/Q 0 1995 American Chemical Society

Reaction of Aminocarbene-Chromium Complexes

Organometallics, Vol. 14, No. 6, 1995 2761

Figure 1. ORTEP drawing of compound 3 showing the atom-labeling scheme. The thermal ellipsoids are drawn at the 30% probability level. and ( C 0 ) & r N a ~ .Details ~ for these syntheses are given in the Experimental Section. In the case of 24a, the two expected E and Z isomers, differing by the position of the sulfur atom with respect to the metal, were formed in 65% yield and were separated by silica gel chromatography. Reaction with Alkynes. Aminocarbene Complexes Derived from Six-, Seven-, and EightMembered Cycloamines: Formation of Bridgehead Lactams. Solid State Structure of Lactam 3. When complex 1 was refluxed in cyclohexane in the presence of diphenylacetylene, the N-ylide complex 2 was obtained as yellow crystals in 65%yield. Heating this complex either in boiling toluene or pyridine led to formation of the metal-free bridgehead lactam 3 in 40% yield. Migration of the alkyl chain from nitrogen to the

Table 1. Selected Bond Distances (A) and Bond Angles (deg) for Compound 3 O(l)-C(lO) N(1)-C(6) C(l)-C(9) C(2)-C(3) C(3)-C(4) C(5)-C(6) C(8)-C(9) C(9)-C(91)

1.216(7) 1.468(7) 1.340(8) 1.527(9) 1.553(9) 1.534(9) 1.517(8) 1.473(8) 122.8(5) 117.5(5) 118.9(5) 116.7(5) 118.4(6) 110.3(5) 111.0(5)

102.1(5) 102.1(5) 125.7(6) 125.7(6) 107.0(5)

N(1)-C( 1) N(l)-C(lO) C(l)-C(ll) C(2)-C(8) C(4)-C(5) C(7)-C(8) C(8)-C(10)

1.420(7) 1.388(7) 1.475(8) 1.561(9) 1.541(9) 1.519(8) 1.528(9) 109.3(5) 111.4(5) 129.7(6) 119.8(6) 115.8(5)

114.2(5) 114.9(5) 111.1(5) 108.5(5) 125.8(5) 127.0(6)

be characterized either free or as their Cr(C0)3 complexes. Minor products were isolated in these two cases: the lactone 7 in the case of complex 4 (vide infra)

1

. ._ 2

3

y carbon could be confirmed by an X-ray analysis carried

out on crystals of 3. The ORTEP projection of this lactam appears in Figure 1, the most important bond distances (A) and bond angles (deg) being gathered in Table 1. Increasing the size of the cycle did not change the course of the reaction: the expected lactams could

and the enamine 12 and its hydrolysis product, the already described ketone g6 in the case of complex 8.

2762 Organometallics, Vol. 14, No. 6, 1995

Parlier et al.

(CO)&r3(

9

‘hc=,Cph_

P

ph-Cr(CO)3 h w + P

Ph h

w

+

R1

0

13a Rl=Me 13b R,=H 13C RI-Ph 13d R1=thienyl

Ch

15

14

Ph

Ph

9

10

*

11

17

16

12

Pyrrolidine and Derivative-Substituted Carbene Complexes: Formation of Pyrroles. When complex 13a was heated in refluxing benzene in the presence of a slight excess of diphenylacetylene for 12 h, a mixture of new complexes and organic products was obtained. They could be separated as such (see the Experimental Section), but for the sake of simplicity the residue of the reaction was treated with pyridine in order to remove the metal. Silica gel chromatography led finally to two organic products. The less polar compound obtained in 25%yield was given the structure 15a: its mass spectrum and elemental analysis confirmed that it was not a classical product arising either from the sole alkyne insertion (one more carbon observed) or from the alkyne and CO insertions (no oxygen present). The lH and 13C NMR spectra were quite

simple: the first spectrum displayed signals for the aromatic protons and for the methylene groups of the pyrrolidine ring system. Moreover, a signal for a deshielded methyl group was present at 6 2.27 ppm. In the second spectrum, the CH2 groups gave signals at 6 43.13,23.75,23.40,and 21.12 ppm, confirming that ringopening with rearrangement probably took place. The structure of the corresponding arene chromium complex 14a was finally assessed by X-ray diffraction study. The ORTEP projection appears in Figure 2, the most important bond distances (A) and bond angles (deg) being collected in Table 2. The figure indeed shows that, in addition to the insertion of the alkyne and of one carbon atom, a major rearrangement took place with migration of the alkyl chain from nitrogen to the inserted carbon atom C(9). The second product (31% yield) was the expected bridgehead lactam 17a resulting from the insertion of

P

C(12)

Figure 2. ORTEP drawing of compound 14a showing the atom-labeling scheme. The thermal ellipsoids are drawn at the 30% probability level. !



Table 2. Selected Bond Distances (A) and Bond Angles (deg) for Compound 14a 1.834(3) 1.834(3) 1.833(3) 2.266(2) 2.207(2) 2.205(3) 1.379(3) 1.376(3) 1.486(3) 1.472(3) 1.469(3) 1.503(4) 1.483(3) 90.0(1) 87.8(1) 87.1(1) 125.3(2) 124.9(2) 121.7(2) 107.3(2) 111.8(2) 110.6(2) 107.4(2) 131.8(2)

1.146(3) 1.150(3) 1.146(3) 2.213(3) 2.216(3) 2.210(2) 1.462(3) 1.370(3) 1.431(3) 1.379(3) 1.502(4) 1.507(4) 179.1(2) 179.4(3) 178.0(2) 109.8(2) 107.9(2) 130.3(2) 107.5(2) 111.7(2) 111.9(2) 120.7(2)

both the alkyne and CO and from the migration of the alkyl chain from nitrogen to the y position. Complexes 13b-d behaved similarly with diphenylacetylene and gave mixtures of pyrrole complexes 14 and pyrroles 15 and of lactam complexes 16 and lactams 17. However, the insertion of 1-phenyl-1-propyne into carbene complex 13c only gave a mixture of the complexed and metal-free bridgehead lactams 19 and 20. In the case of complex 21, derived from perhydroindole, the pyrrole 22 and its complex 23 were the major

19

20

products of the reaction (31% yield). The structure of

Q3-

PhCiCPh

(cO)scrd H

21

H

H

23

22

22 could again be ascertained by an X-ray analysis. The ORTEP view appears in Figure 4, the most important bond distances (A) and bond angles (deg) being displayed in Table 4. Notice here that in the case of complex 13b the same lactone 7 as from complex 4 could be isolated and fully characterized as its Cr(C0)3 complex 18, the hydrolysis product of the aminofuran

18a

18

Figure 3. ORTEP drawing of compound 18 showing the atom-labeling scheme. The thermal ellipsoids are drawn at the 30% probability level.

Parlier et al.


Table 3. Selected Bond Distances (A) and Bond Angles (deg) for Compound 18 1.815(6) 1.823(6) 1.825(6) 2.242(5) 2.215(6) 2.213(6) 1.430(7) 1.495(7) 1.460(7) 1.471(6)

Cr(l)-C(ll) Cr(l)-C(12) Cr(l)-C(13) Cr(l)-C(21) Cr(l)-C(23) Cr(l)-C(25) 0(1)-C(1) C(l)-C(2) C(2)-C(21) C(3)-C(31) C(l2)-Cr(l)-C(ll) C(l3)-Cr(l)-C(ll) C(l3)-Cr(l)-C(l2) C(4)-0(l)-C(l) C(3)-C(2)-C(1) C(21)-C(2)-C(3) C(31)-C(3)-C(2) C(3)-C(4)-0(1) 0(2)-C(4)-C(3)

C(ll)-O(11) C(12)-0(12) C(13)-0(13) Cr(l)-C(22) Cr(l)-C(24) Cr(l)-C(26) 0(1)-C(4) C(2)-C(3) C(3)-C(4) C(4)-0(2)

87.9(3) 85.5(3) 88.7(3) 110.1(4) 108.9(4) 130.8(5) 130.8(5) 108.3(5) 128.4(6)

1.163(7) 1.162(7) 1.144(7) 2.200(5) 2.196(5) 2.198(6) 1.344(7) 1.334(7) 1.491(7) 1.179(7)

O(ll)-C(ll)-Cr(l) 0(12)-C(12)-Cr(l) 0(13)--C(l3)-Cr(l) C(2)-C(l)-O(l) C(21)-C(2)-C(l) C(4)-C(3)-C(2) C(31)-C(3)-C(4) 0(2)-C(4)-0(1)

179.1(6) 179.5(6) 178.0(6) 104.9(4) 120.3(5) 107.8(5) 121.4(5) 123.3(6)

Table 4. Selected Bond Distances (A) and Bond Angles (deg) for Compound 22 1.364(4) 1.460(4) 1.509(4) 1.510(5) 1.511(5) 1.524(4) 1.497(4) 1.430(4)

C(l)-C(13) N(2)-C(ll) C(4)-C(lO) C(5)-C(10) C(7)-C(8) C(9)-C(lO) C(ll)-C(12)

108.9(2) 109.3(2) 110.4(2) 113.6(3) 111.0(3) 112.3(2) 111.8(2) 110.1(3) 119.7(3) 132.2(3) 106.5(3)

Figure 4. ORTEP drawing of compound 22 showing the atom-labeling scheme. The thermal ellipsoids are drawn at the 30% probability level. complex 18a. Its ORTEP projection appears in Figure 3, the most important bond distances (A) and bond angles (deg) being gathered in Table 3. Thiazolidine-Derived Carbene Complexes 24a and 24b. Since, in the case of the two rotamers 24a-2 and 24a-E, products arising from the cleavage of two

cs NJ

1.368(4) 1.380(3) 1.528(4) 1.525(4) 1.528(5) 1.537(4) 1.373(4) 125.2(2) 124.8(2) 109.8(3) 111.0(3) 112.1(3) 111.0(3) 113.8(3) 111.4(3) 107.4(2) 107.8(2)

PhCiCPh

24a +Me 24b RiSPh 24a-2

24a-E

different carbon-nitrogen bonds, N-C(3) or N-C(4), could be expected, their structures were accurately determined by X-ray crystallography and the alkyne insertion reaction was carried out on the two complexes separately. Crystals of the less polar complex could be grown: as shown on the ORTEP projection provided in Figure 5 it corresponds to the E isomer. In agreement with the structures already established for other aminocarbene complexes of chromium, the bond distances are typical for such a complex with a short nitrogencarbon bond (N(l)-C(l) = 1.300(4)& and a long metalcarbon bond (Cr-C(l) = 2.123(3) A). The bond distances (A)and bond angles (deg) are displayed in Table 5. However, no variation in the product distribution was observed: both isomers reacted with diphenylacetylene and led to the same mixture of pyrrole 25a and of its Cr(C0)3 complex. According t o the lH NMR spectrum, 25a consisted of a mixture of isomers, one of them being largely predominant: for one isomer the isolated CH2

,.

Dh

27 R1=Ph

25 +Me X-S, Y=CH, X=CH.. Y=S

PhJO

+

+'&Ph Ph 9 R,=Me

28

Ph

& 29 Ph

group gave a signal at 6 3.93 ppm, and for the other isomer it appeared at 6 3.90 ppm. In contrast to pyrroles 15, pyrroles 25a appeared to be very unstable, degradation of the product being observed both in chlorinated solvents and on silica gel. Thus the best yield (25%) was observed upon direct silica gel flash chromatography of the reaction residue. That both isomers gave the same result was probably linked to



Figure 5. ORTEP drawing of compound 24a showing the atom-labeling scheme. The thermal ellipsoids are drawn at the 30% probability level. Table 5. Bond Distances (A>and Bond Angles (dep) for Compound 24a 2.123(3) 1.895(3) 1.892(3) 1.786(4) 1.139(4) 1.146(4) 1.138(4) 1.488(4) 1.510(4) 89.0(1) 174.6(1) 94.9(1) 89.2(1) 90.4(1) 88.5(1) 90.8(1) 177.6(2) 178.1(3) 179.4(3) 177.3(3) 90.1(2) 124.4(2) 129.5(2) 112.8(3) 108.5(3)

1.888(3) 1.864(3) 1.893(3) 1.785(4) 1.130(4) 1.134(4) 1.300(4) 1.482(4) 1.487(5) 92.5(1) 86.4(1) 177.9(1) 89.5(1) 91.2(1) 87.6(1) 90.1(1) 176.3(3) 177.6(3) 124.6(2) 111.1(2) 117.6(2) 107.9(2 105.2(2)

the interconversion of the isomers during the insertion reaction: indeed, heating 24a-E or 24a-Z in benzene for 12 h led to a 50150 mixture of the two isomer^.^ Complex 24b (R1 = Ph), obtained as a 40/60 mixture of EIZ isomers behaved differently: no pyrrole could be detected. Instead, the major products of the reaction appeared to be the aminofuran 26b and its Cr(C0)3 complex. Treatment of the crude reaction product in (4)Rudler, H.; Parlier, A,; Yefsah, R.; Denise, B.; Daran, J. C.; Vaissermann, J.; Knobler, C. J . Organomet. Chem. 1988,358, 245. (5) Imwinkelried, R.; Hegedus, L. S. Organometallics 1988,7 , 702.

boiling pyridine, after silica gel chromatography, gave 26b in 41% yield together with small and variable amounts of its oxidation product, the ketoamide 27. The lH NMR spectrum of 26b confirmed the presence of the thiazolidine ring system, with signals at 6 4.35 (NCHzS), 3.62, and 3.10 ppm (2CHz). The 13CNMR spectrum was again typical for such a structure with a signal at 6 151.3 ppm for the NCO carbon and a signal a t 6 109 ppm for the second carbon of the furan linked to oxygen. The spectroscopic data of 27 agreed with those of other ketoamides already isolated from aminofurans: the 13C NMR spectrum disclosed signals for the two carbonyl carbons at 6 197.04 and 168.06 ppm. Finally, small and amounts of the benzannulation products 28 (11%) 29 (7%) were also isolated.* In order to get a better insight into the mechanism of this reaction, attempts were made to isolate the presumable N-ylide which might be formed prior to the rearrangement reaction. However, heating the alkyne and the starting complex 24b in refluxing cyclohexane led directly t o the formation of 26b, the complexed aminofuran. Pyrroline and Azetidine-Substituted Carbene Complexes 30a,b, 33a-e, and 36. Under the same conditions as for the pyrrolidine-substituted carbene complexes, no bridgehead lactams were isolated starting from the pyrrolidine-substituted carbene complexes. Thus, complexes 30a,b led to the lactams 32a and 32b in respectively 61% and 43% yields. However, in the case of 30a, a less polar compound could be detected. Both its mass spectrum (mlz = 347) and its proton NMR spectrum, with signals at 6 3.95 and 3.31 ppm for the bwo CH2 groups, were consistent with a structure such as 31a. A similar result was observed in the case of 30b which led to trace amounts of 31b. Likewise,

Parlier et al.


30a R-Ph 30b R-Thienyl

37

36

d

0

318 31b

32b

starting from azetidine-substituted carbene complexes 33a-d, no bridgehead lactams were isolated. Thus,

-

v

raphy. The spectroscopic data of 34c were in accordance with those of the pyrroles so far isolated: the mass spectrum agreed with the absence of oxygen, whereas the 'H NMR spectrum depicted signals for three distinct CHz groups, at 6 4.08 (NCHz), 3.11, and 2.56 ppm. Surprisingly, whereas the phenyl-substituted azetidine carbene complex 33d gave the insertion product 35d as a mixture of two isomers, no reaction except for decomposition of the starting complex was observed in the case of complex 33e.

PhCECPh

Discussion

R1

33a R1= H, R -H

33b R,=Me,&=H 3 3 RlsPh, ~ R2=H 33d R,=Me, R2=Ph 33e Rl=H, R2=Ph

Ph L

P

wRz

h

0

RJ

35a Rl=H, R =H 35b R,=Me, h2=H 3 5 RltPh, ~ R& 35d +Me, R2=Ph

when 33b was heated in benzene in the presence of diphenylacetylene, the metal-free substituted pyrrolizidine 35b was obtained in 40% yield as a white solid. The IR spectrum ( Y C O , 1675 cm-l) as well as the 13C were in agreement NMR spectrum (6 173.7 ppm ((20)) with the presence of an unsaturated lactam. The 13C NMR spectrum disclosed signals for a quaternary N-C carbon at 6 72.22 ppm, for a NCHz group at 6 41.34 ppm, for two methylene groups at 6 35.15 and 28.40 ppm, and finally for the angular methyl group at 6 22.24 ppm. Similar results were observed for complexes 38a,c,d and 36, which gave the corresponding lactams 35a,c,d and 37. A slight difference in behavior was, however, observed for complex 33c since small amounts (1.8%) of the corresponding pyrrole 34c could be detected and isolated upon careful silica gel chromatog-

Up t o now, most of the products obtained upon insertion of the alkynes into aminocarbene complexes of chromium could be derived from the Cr(C013stabilized betaine 39 (Scheme 11, one of the limiting forms of the isolated intermediate, which can also be considered as the vinylog of the Stevens betaine 45 (Scheme 2L9 Indeed and without taking into account the presence of the metal, successive (1,5) migrations of the alkyl group R3 led either to 41 via 40 or t o 44 via 42 and 43 (Scheme 1). However, products derived from 42 and resulting thus from the migration of the alkyl group on the central atom of the ketene function were still missing, although in the case of organic betaines 45, products arising from the migration of an alkyl group from nitrogen to the carbon atom C(3) were observed (Scheme 2). Thus 45 (R1 = R2 = R3 = Me, R2 = CHzPh) led, in addition to the expected (1,2) migration product, t o the hydroxy ketone 47 via 46.1° This gap has now been filled since pyrroles of the general structure 49 could be isolated during the insertion of alkynes into pyrrolidine-substituted carbene complexes of chromium. The structures of 14a and 22 clearly indicate that ring opening took place together with the migration of the alkyl chain on carbon C(5) (39 42). However, in contrast to the iminium derivative 46, which gave 47 upon hydrolysis, 42 rearranges according to another pathway to give the pyrrole 49: loss of oxygen is indeed observed. Although the exact mechanism of this transformation is not known, one can tentatively assume that the metal is involved in this

-

Scheme 1

rn :r(CO), I

I

/

~ 3 1

44

42

41



Scheme 2

carbene complexes of iron.12 More interestingly, the formation of furans is not limited t o the case of aminocarbene complexes: indeed, Wulff and his co-workers observed the formation of alkoxyfurans from alkoxycarbene complexes of chromium and m01ybdenum.l~ Labeling experiments clearly showed that migration of the alkoxy group from C(2) to C(5) took place. (Scheme 5, X = 0). However, a mechanism via ylide complexes such as 39 (X = 0 ) had been excluded. Let us again consider the Stevens rearrangement: a third reaction14 which had been observed in the case of alkyl groups of low propensity for migration, was indeed the C(2)-N(1) bond rupture with formation of a tertiary amine together with products 51 formally derived from the carbenes 50. (Scheme 4). Applied to betaine 39 such a bond rupture would lead to the alkenone carbene complexes 52 (Scheme 4)or 54 (Scheme 5). Yet is is known that such intermediates which can be generated either photochemically from acetylcyclopropenes15 or via carbene complexes from alkynyl diazo esters? rearrange to furans. Thus, a mechanism which could account for the formation of both alkoxy and aminofurans might involve free- or metal-stabilized alkenone carbenes is outlined in the general Scheme 5: interaction of the heteroatom with the central carbon atom of the ketene function of 38 might lead to a metal-stabilized ylide 53: for Rz groups of low propensity for the migration, a metalinduced C(2)-X bond rupture could take place leading to a new carbene complex 54. This complex might then undergo either of the two following transformations: (1) If the reaction is carried out under CO (as for the aminocarbene complexes of iron), CO insertion giving the ketene complex 55 followed by an electrocyclization reaction would lead t o the pyrone 56. Such products have indeed been observed in the case of aminocarbene complexes of iron.12 (2) Interaction of the carbonyl group with the carbene function in 54 followed by a haptotropic shift of the metal would then lead to the furan complexes 58 via 57. That the interaction between X and the ketene function is less favored for X = 0 than for X = NR appears clearly since cyclobutenones 59 are present in almost all of the reaction mixtures obtained during the insertion of alkynes into alkoxycarbene complexes of chromium as the result of a favored cycloaddition reaction of the two carbon-carbon double bonds in 38.17 The formation of aminocyclobutenonesfrom aminocarbene complexes has, to the best of our knowledge, not been observed.

45

Scheme 3 P2

42 R2

R2

48

-49

last reaction: low-valent metal deoxygenation reactions are indeed known, and moreover, Cr(0)-mediated carbon-oxygen bond cleavages have been observed.ll A possible mechanism for this transformation could thus involve the formation of 48 via an intramolecular nucleophilic addition followed by a Cr(0)-mediated deoxygenation reaction (Scheme 3). That pyrroles are preferentially observed in the case of pyrrolidine-substituted carbene complexes might be due to the formation of a stable six-membered ring system upon the first (1,5)migration of the alkyl chain from nitrogen t o the carbonyl carbon atom (39 42, Scheme 2, R2R3 = (CHZ)~) followed by the irreversible deoxygenation reaction (42 49). Comments on the Mechanism of Formation of Furans. A last intriguing point concerns the formation of aminofurans during these alkyne insertion reactions. Aminofurans have been observed in several instances during the reaction of aminocarbene complexes of chromium with alkynes: this was, for example, the case for complexes derived from N-methylaniline.8 In the present report, complex 24b gave as the main product the aminofuran 26 and its derivative 27 whereas complexes 13b and 4 gave the lactone 18, the hydrolysis product of the aminofuran 18a. These types of products had also been obtained by Semmelhack from amino-

-

-

Scheme 4

45

39

50

51

52

2768

Parlier et al.

Organometallics, Vol. 14, No. 6, 1995 Scheme 5

59

39

R:,

R2

50

Conclusion Although several points concerning the interaction of aminocarbene complexes of chromium with alkynes have to be examined further, it is now clear that this reaction has many points in common with the Stevens rearrangement of acyl-stabilized nitrogen ylides. Most of the products which were expected from such a rearrangement have now been isolated or detected, in some cases in low yield.

Experimental Section General Methods. 'H NMR and I3C NMR spectra were recorded on a JEOL GX 400 or on a Bruker WM 200 spectrometer. IR spectra were recorded on a Perkin-Elmer 1420 spectrophotometer. Mass spectra were recorded on a ZAB HSQ (Fisons) instrument. Column chromatography was performed with Merck silica gel (70-230 mesh) using various ratios of ethyl acetateflight petroleum ether or dichloromethand light petroleum ether as eluent. All reagents were obtained from commercial suppliers and used as received. Reactions were performed under an argon atmosphere in carefully dried glassware. Benzene, tetrahydrofuran (THF), and diethyl ether were distilled from sodiumhenzophenone ketyl under a nitrogen atmosphere. Dichloromethane (CH2C12)was distilled from calcium hydride under a nitrogen atmosphere. Aminocarbene complexes 13a were prepared according to a previous rep01-t.~ (CO)&r=C(Ph)N(CH&(1) was obtained from ( C 0 ) 5 C F C(Ph)OEt and piperidine in diethyl ether upon evaporation of the volatiles under vacuum; yield 66%; yellow crystals: mp 81 "C; IR (CHC13)2020,1970,1920 cm-l; 'H NMR (200 MHz, CDC13) b 7.35-6.60 (m, 5H, ArH), 4.45 (t,2H, NCHz), 3.37 (t, 2H, CH2); 13C NMR (50 MHz, CDC13) 6 271.01 (CFC), 224.05, 217.23 (CO), 128.46-118.99 (Ar),61.47, 55.66 (NCHz), 27.99, (6) Denise, B.; Dubost, P.; Parlier, A.; Rudler, M.; Rudler, H.; Daran, J. C.; Vaissermann, J.; Delgado, F.; Arevalo, A. R.; Toscano, R. A.; Alvarez, C. J . Organomet. Chem. 1991,418, 377. (7) Casey, C. P.; Shusterman, A. J.; Vollendorf, N. W.; Haller, K. J. J . A m . Chem. SOC.1982,104, 2417. (8) Bouancheau, C.; Parlier, A.; Rudler, M.; Rudler, H.; Vaissermann, J.; Daran, J. C. Organometallics 1994, 13, 4708. (9) Stevens, T. S.; Creighton, E. M.; Gordon, A. B.; Mac Nicol, M. J . Chem. SOC.1928, 3193. (10)Chantrapomma, K.; Ollis, W. D.; Sutherland, I. 0. J . Chem. SOC.,Perkin Trans. 1 1983, 1049 and references cited therein.

57

\ 56

23.96 (3 CH2). Anal. Calcd for C17H15N05Cr: C, 55.89; H, 4.11; N, 3.83. Found: C, 55.88; H, 4.06; N, 3.70. N-Ylide Complex Cs0H2aN0&r (2) was obtained upon refluxing a solution of complex 1 (6.5 g, 17.6 mmol) and diphenylacetylene (4.7 g, 26.4 mmol) in cyclohexane (175 mL) for 24 h. Filtration of the precipitate gave complex 2 (5.8 g, 64.8%)as a yellow powder: mp 212 "C; IR (CHC13) 1950,1870, 1700 cm-'; lH NMR (200 MHz, CDC13) 6 7.28-7.11 (m, 10H, ArH), 5.40-4.85 (m, 5H, ArCr), 3.65 (m, 2H, NCHd, 3.30 (m, 2H, NCHz), 1.61 (m, 4H, 2 CH2); 13C NMR (100 MHz, CDCl3) 6 234.01 (CO), 170.05 (CO), 134.13, 130.69-127.47, 114.05 (C=C, Ar), 95.71,88.50,86.86 (ArCr), (NC(Ph)),55.99 (NCHZ), 20.98, 20.23 (CH2). HRMS for C30H25N0&r(Mf). Calcd 515.1188. Found: 515.1188. Lactam 3 and lactam complex 3a were obtained upon refluxing complex 2 (0.5 g, 0.97 mmol) in anhydrous toluene for 18 h. Workup as usual gave lactam 3 (0.49 g, 28%),a white solid which was recrystallized from CH&lz/hexane: mp 195196 "C; IR (CHC13) 1700, 1590 cm-l; 'H NMR (200 MHz, CDC13) 6 7.42-6.86 (m, 15H, Ar), 4.18 (m, l H , NCH), 3.23 (m, l H , NCH), 2.98 (m, l H , COCCH), 2.70 (m, l H , COCCH), 2.17 (m, lH), 1.78 (m, 2H), 1.45 (m, 3H); 13CNMR (50 MHz, CDC13) 6 188.68 (CO), 141.98-123.44 (C=C, Ar), 62.52 (COC(Ph)), 45.98 (NCH2),43.17, 35.43, 25.81, 25.57 (CH2). Anal. Calcd for C27H25NO:C, 85.49; H, 6.60; N, 3.69. Found: C, 85.06; H, 6.57; N, 3.59. Lactam complex 3b was also obtained (0.28 g, 12%); yellow crystals: mp 223 "C; 'H NMR (200 MHz, CDC13) 6 7.35-7.05 (m, 10H, ArH), 5.45 (m, 2H, ArCr), 5.25 (m, l H , ArCr), 5.02 (m, 2H, ArCr), 4.19 (m, l H , NCH), 3.26 (m, l H , NCH), 2.85 (m, lH), 2.55 (m, lH), 1.84-1.24 (m, 4H); (11)Tumer, S. U.; Herndon, J . W.; Mac Mullen, L. A. J . Am. Chem. SOC.1992, 114, 8394. (12) Semmelhack, M. F.; Park, J. Organometallics 1986, 5 , 2550. (13) McCallum, J. S.; Kunng, F. A,; Gilbertson, S. R.; Wulff, W. D. Organometallics 1988, 7, 23467 (14) Jemison, R. W.; Mageswaran, S.; Ollis, W. D.; Sutherland, I. 0.;Thebtaranonth, Y. J . Chem. SOC.,Perkin Trans. 1 , 1981, 1154. (15)Padwa, A.; Akiba, M.; Chou, C. S.; Cohen, L. J . Org. Chem. 1982, 47, 183. (16) Padwa, A,; Kinder, F. R. J . Org. Chem. 1993, 58, 21. (17) Wulff, W. D.; Bax, B. M.; Brandvold, T. A.; Chan, K. S.; Gilbert, A. M.; Hsung, R. P.; Mitchell, J.; Clardy, J . Organometallics 1994,13, 102 and references cited therein. (18)Watkins, D. J.; Carruthers, J. R.; Betteridge, P. W. Crystals User Guide; Chemical Crystallography Laboratory, University of Oxford: Oxford, England, 1985. (19) International Tables for X-ray Crystallography; Kynoch Press: Birmingham, U.K, 1974; Vol. 4. (20) Sheldrick, G. M. SHELXS 86, Program for Crystal Structure Solution; University of Gottingen: Gottingen, Germany, 1986.



Table 6. Fractional Parameters for Compound 3 atom

xla

O(1) 0.6436(4) N(1) 0.4227(5) 0.3058(6) C(1) C(2) 0.4553(6) 0.3629(7) C(3) C(4) 0.4099(7) C(5) 0.3488(7) C(6) 0.4151(6) C(7) 0.5574(6) 0.4674(6) C(8) C(9) 0.3286(6) 0.5281(6) C(10) 0.1812(6) C(11) C(12) 0.0577(6) C(13) -0.0585(7) (314) -0.0510(8) 0.0686(8) (315) C(16) 0.1862(6) C(72) 0.5532(7) 0.6390(8) C(73) (374) 0.7274(8) 0.7364(8) C(75) C(76) 0.6480(8) C(91) 0.2346(6) 0.1641(7) C(92) C(93) 0.0703(7) 0.0486(8) C(94) C(95) 0.1172(9) C(96) 0.2131(8)

Ylb 0.2279(4) 0.2910(4) 0.2977(5) 0.0644(6) 0.0303(6) 0.0504(6) 0.1517(6) 0.2681(6) 0.2227(6) 0.1946(5) 0.2507(6) 0.2407(6) 0.3503(6) 0.2928(6) 0.3414(7) 0.4457(7) 0.5042(7) 0.4582(6) 0.3313(6) 0.3622(8) 0.2839(8) 0.1786(8) 0.1466(7) 0.2534(6) 0.3527(6) 0.3531(7) 0.2590(8) 0.1614(8) 0.1579(7)

zlc

0.2445(2) 0.2351(3) 0.1751(3) 0.1445(4) 0.1977(4) 0.2846(4) 0.3204(4) 0.3142(4) 0.0739(4) 0.1290(4) 0.1112(3) 0.2084(4) 0.1900(3) 0.1715(4) 0.1885(4) 0.2224(4) 0.2399(4) 0.2236(4) 0.0438(4) -0.0047(5) -0.0229(5) 0.0064(5) 0.0546(4) 0.0363(4) 0.0102(4) -0.0601(4) -0.1030(4) -0.0810(5) -0.0106(4)

U(eq) 0.0472 0.0335 0.0348 0.0446 0.0495 0.0494 0.0471 0.0402 0.0398 0.0341 0.0344 0.0378

U(iso)

0.038(2) 0.045(2) 0.060(2) 0.063(2) 0.057(2) 0.046(2) 0.056(2) 0.0 75 (2) 0.073(2) 0.077(3) 0.067(2) 0.041(2) 0.048(2) 0.059(2) 0.067(2) 0.080(3) 0.065(2)

Table 7. Fractional Parameters for ComDound 14a xla

0.42595(6) 0.1824(4) 0.0294(3) 0.4885(4) 0.5266(4) 0.5084(4) 0.5574(4) -0.1221(3) -0.1609(3) -0.0138(3) 0.1198(3) -0.3326(4) -0.2451(4) -0.1467(4) -0.0423(5) 0.1174(4) 0.0484(3) 0.0086(3) 0.1763(4) 0.1987(5) 0.0539(5) -0.1135(5) -0.1366(4) 0.3007(3) 0.4714(4) 0.6478(4) 0.6560(4) 0.4863(4) 0.3107(4)

Yfb 0.17187(4) 0.1086(3) 0.0706(3) 0.0328(3) -0.0552(2) 0.0467(3) -0.0345(2) 0.4275(2) 0.5375(2) 0.5350(2) 0.4187(2) 0.6385(3) 0.3920(3) 0.2808(3) 0.1670(3) 0.2249(3) 0.3539(2) 0.6390(2) 0.7110(3) 0.8089(3) 0.8378(3) 0.7689(3) 0.6699(3) 0.3777(2) 0.3324(3) 0.3009(3) 0.3127(3) 0.3545(3) 0.3846(2)

zlc

0.23322(3) 0.2435(2) 0.2491(2) 0.3387(2) 0.4046(2) 0.1693(2) 0.1314(2) 0.4046(1) 0.3268(2) 0.2607(2) 0.2998(1) 0.3251(2) 0.4905(2) 0.5663(2) 0.5313(2) 0.4595(2) 0.3886(2) 0.1691(2) 0.1427(2) 0.0569(2) -0.0040(2) 0.0213(2) 0.1067(2) 0.2534(2) 0.3004(2) 0.2551(2) 0.1616(2) 0.1130(2) 0.1581(2)

0.0410 0.0619 0.0458 0.0705 0.0440 0.0672 0.0349 0.0351 0.0322 0.0312 0.0481 0.0431 0.0503 0.0562 0.0429 0.0331 0.0345 0.0456 0.0530 0.0513 0.0533 0.0461 0.0332 0.0401 0.0460 0.0484 0.0442 0.0383

I3C NMR (50 MHz, CDC13) 6 232.86 (CO), 186.01 (CO), 142.79, 134.25,129.53-127.34,121.27 (C=C, Ar), 108.93,94.20,93.91, 93.49, 89.99 (ArCr), 59.22,46.50,46.32, 35.32, 26.18,24.39 (5 CH2). Lactam 3 (0.14 g, 40%) could also be obtained upon refluxing complex 2 (0.5 g, 0.97 mmol) in pyridine (30 mL) for 12 h followed by workup as usual. (CO)&r=C(H)N(CHz)a (4) was obtained from formylheptamethylenimine and (CO)&rNaz according to the method of Hegedusrefin 70% yield as yellow crystals: mp 36-37 "C; IR (CHC13)2050,1990,1930 cm-I; 'H NMR (200 MHz, CDC13) 6 10.49 (s, l H , Cr=CH), 4.14 (t, J = 6 Hz, 2H, NCHz), 3.27 (t,J = 6 Hz, 2H, NCHz), 2.0-1.67 (m, 8H, 4CH2); I3C NMR (50 MHz, CDC13) 6 262.63 (Cr=O), 224.23, 217.76 (CO), 65.72, 58.06 (NCH2),29.37, 28.10, 27.20, 26.14 (CH2). Anal. Calcd

Table 8. Fractional Parameters for Compound 18 atom

xla

0.06361(7) 0.0089(6) -0.0272(5) -0.0508(6) -0.1244(5) -0.0664(5) -0.1492(4) 0.2817(5) 0.2247(6) 0.2895(5) 0.3751(5) 0.3698(7) 0.4315(5) 0.2544(5) 0.2619(5) 0.2304(5) 0.1865(5) 0.1774(6) 0.2081(5) 0.4611(5) 0.5402(6) 0.6144(6) 0.6131(5) 0.5396(6) 0.4645(5)

zlc

0.0009(1) -0.0978(5) -0.1616(4) 0.0961(5) 0.1562(4) -0.0508(5)

-0.0849(5) 0.1864(3) 0.1803(4) 0.0863(4) 0.0438(4) 0.1075(5) 0.0959(4) 0.0553(4) -0.0540(5) -0.0838(5) -0.0062(7) 0.1007(6) 0.1309(5) -0.0502(4) -0.0645(5) -0.1529(6) -0.2346(6) -0.2202(5) -0.1288(4)

0.46411(6) 0.3669(5) 0.3056(4) 0.4058(5) 0.3687(5) 0.5481(5) 0.5983(4) 0.1335(3) 0.2373(5) 0.2900((4) 0.2225(4) 0.1215(5) 0.0433(3) 0.3987(4) 0.4319(4) 0.5367(5) 0.6068(4) 0.5766(5) 0.4714(5) 0.2338(4) 0.3224(4) 0.3316(5) 0.2544(8) 0.1653(5) 0.1533(4)

Ueq) 0.0361 0.0475 0.0708 0.0572 0.0788 0.0479 0.0735 0.0557 0.0464 0.0303 0.0352 0.0514 0.0611 0.0317 0.0397 0.0469 0.0542 0.0525 0.0438 0.0365 0.0467 0.0583 0.0572 0.0509 0.0430

Table 9. Fractional Parameters for Compound 22 atom C(1) N(2) C(3) C(4) C(5) C(6) C(7) C(8) C(9) C(10) C(11) C(12) C(13) C(14) C(15) C(16) C(17) C(18) C(19) C(20) C(21) C(22) C(23) C(24) C(25)

xla

ylb

zlc

0.1839(3) 0.2203(2) 0.1588(3) 0.1963(3) 0.3839(3) 0.3665(3) 0.4243(4) 0.3726(3) 0.3879(3) 0.3365(3) 0.3337(2) 0.3666(2) 0.2709(2) 0.4780(3) 0.5945(3) 0.6952(3) 0.6842(3) 0.5704(3) 0.4679(3) 0.2615(3) 0.1474(3) 0.1354(3) 0.2364(3) 0.3495(3) 0.3633(3)

-0.0559(3) 0.0535(2) 0.1741(3) 0.2626(3) 0.3707(3) 0.3414(3) 0.2171(3) 0.1120(3) 0.1393(3) 0.2682(3) 0.0367(3) -0.0862(3) -0.1457(3) -0.1460(3) -0.0932(3) -0.1460(4) -0.2518(4) -0.3071(3) -0.2547(3) -0.2757(3) -0.3341(3) -0.4533(3) -0.5164(3) -0.4606(3) -0.3416(3)

-0.0148(2) 0.0283(2) 0.0085(2)

0.0857(2) 0.1807(2) 0.2730(2) 0.3049(2) 0.2405(2) 0.1465(2) 0.1133(2) 0.0843(2) 0.0773(2) 0.0143(2) 0.1319(2) 0.1389(2) 0.1949(2) 0.2416(2) 0.2337(2) 0.1795(2) -0.0185(2) -0.0404(2) -0.0760(2) -0.0911(2) -0.0687(2) -0.0329(2)

'

U(ed 0.0442 0.0427 0.0495 0.0525 0.0585 0.0641 0.0648 0.0531 0.0424 0.0478 0.0398 0.0384 0.0384 0.0401 0.0485 0.0553 0.0592 0.0577 0.0493 0.0406 0.0489 0.0564 0.0558

0.0531 0.0474

for Cl2Hl3NO6Cr: C, 47.52; H, 4.29; N, 4.62. Found: C, 47.72; H, 4.23; N, 4.50. Lactam complex 5, lactam 6, and lactone 7 were obtained upon refluxing a solution of complex 4 (2.5 g, 9 mmol) and diphenylacetylene (2 g, 11mmol) in benzene (100 mL) for 12 h. Workup as usual followed by silica gel chromatography first gave complex 5 (1.5 g, 40%) as yellow crystals: mp 177178 "C; IR (CHC13) 1970,1890,1710 cm-l; 'H NMR (200 MHz, CDC13)6 7.30 (m, 5H, ArH), 6.88 (s, l H , Cr=CH), 5.60 (9, 2H, ArCr), 5.31 (9, l H , ArCr), 5.07 (m, 2H, ArCr), 4.00 (m, l H , NCH), 3.29 (m, l H , NCH), 2.59 (m, l H ) , 2.20 (m, l H ) , 1.78 (m, 4H), 1.26 (m, 4H); I3C NMR (50 MHz, CDC13) 6 232.81 (CO), 179.02 (CO), 133.67-122.44 (C=C, Ar), 95.44-89.98 (ArCr), 58.50 (PhCCH), 43.80 (NCHz), 39.54, 26.32, 25.78, 21.83 (CH2). Anal. Calcd for C25H23N04Cr: C, 66.22; H, 5.07; N, 3.09. Found: C, 65.54; H, 4.98; N, 2.94. Heating complex 5 in pyridine gave the lactam 6 as a white solid: mp 180-181 "C; IR (CHC13) 1720 cm-l; 'H NMR (200 MHz, CDC13) d 7.14 (m, 10H, ArH), 6.62 (s, l H , =CH), 3.80 (m, l H , NCH), 2.74 (m, l H , NCH), 2.24 (m, 2H, PhCCHZ), 1.64 (m, 8H, 4 CH2); I3C NMR (50 MHz, C&) 6 180.65 (cO),139.63-123.47 (C=C, Ar), 60.07 (PhC), 42.82 (NCH2), 35.11, 26.20, 25.86, 21.06

2770 Organometallics, Vol. 14, No. 6, 1995 Table 10. Fractional Parameters for Compound 24a atom xla Ylb zlc U(eq) U(iso) Cr(1) 0.25249(6) 0.15617(4) 0.41079(4) 0.0392 0.459i(i) 0.4818ii8j 0.0696 S(1) -0.2547(1) O(11) 0.2059(3) -0.0631(2) 0.5198(2) 0.0767 0.3658(2) 0.2887(2) 0.0776 O(12) 0.3035(4) 0.0441(3) 0.2971(2) 0.0710 O(13) 0.5058(3) 0.2191(3) 0.5748(2) 0.0800 O(14) 0.5197(3) 0.0760(2) 0.2470(2) 0.0771 O(15) -0.0054(4) 0.3016(2) 0.4775(2) 0.0385 N(1) -0.0304(3) 0.2348(2) 0.5038(2) 0.0397 C(1) 0.0903(3) 0.2170(4) 0.6183(2) 0.0584 C(2) 0.1184(4) 0.3569(3) 0.5510(2) 0.0526 C(3) -0.1304(4) 0.3319(3) 0.3702(2) 0.0542 C(4) -0.0872(4) 0.3773(3) 0.3678(3) 0.0646 C(5) -0.2543(5) 0.0204(3) 0.4802(3) 0.0521 C(11) 0.2225(4) 0.2895(3) 0.3365(3) 0.0509 C(12) 0.2814(4) 0.0863(3) 0.3402(2) 0.0519 C(13) 0.4088(4) 0.19799(3) 0.5129(2) 0.0517 C(14) 0.4190(4) 0.1080(3) 0.30993(3) 0.0530 C(15) 0.0888(4) 0.162(3) 0.638(3) 0.084(4) H(21) 0.194(4) 0.084(4) 0.207(3) 0.646(3) H(22) 0.027(4)) 0.287(3) 0.651(3) 0.084(4) H(23) 0.167(4) 0.084(4) 0.298(3) 0.575(3) H(31) -0.193(4) 0.397(3) 0.603(3) 0.084(4) H(32) -0.064(4) 0.084(4) 0.267(3) 0.325(3) H(41) -0.086(4) 0.084(4) 0.385(3) 0.344(3) H(42) -0.013(4) 0.084(4) 0.428(3) 0.310(3) H(51) -0.283(4) 0.316(3) 0.370(3) 0.084(4) H(52) -0.328(4) '

(CH2). MS for Cz2H23N0. Calcd 317 (mlz). Found 317. Lactone 7 (0.21 g, lo%), a white solid, was also obtained: mp 137 "C; IR (CHC13) 1750 cm-l; IH NMR (200 MHz, CDC13) 6 7.49-7.34 (m, 10H, ArH), 4.34 (s, 2H, OCH2); 13C NMR (50 MHz, CDC13) 6 173.2 (CO), 155.34, 133.0-123.1 (C=C, Ar), 69.70 (OCH2). MS for C16H1202. Calcd 236. Found 236. (CO)&r=C(Me)N(CH2)7(8) was obtained from acetylheptamethylenimine according to the method of Hegedus5 in 36% yield as a yellow solid: mp 82 "C; IR (CHC13)2040,1965,1920 cm-l; IH NMR (200 MHz, CDC13) 6 4.29 (m, 2H, NCHz), 3.83 (m, 2H, NCHz), 2.79 (s, 3H, CH3), 2.01 (m, 2H, CH21, 1.77 (m, 4H, CH2), 1.30 (m, 4H, CH2); NMR (50 MHz, CDC13) 6 272.59 (CFC), 223.78,218.15 (CO), 66.66,52.43 (NCHd, 40.11 (CH3), 27.50, 27.06, 26.17, 25.60, 23.08 (CH2). Anal. Calcd for C14H17N05Cr:C, 50.75; H, 5.13; N, 4.23. Found: C, 50.90; H, 5.15; N, 4.22. Lactam complex 10, lactam 11, and enamine 12 were obtained upon heating complex 8 (2 g, 6 mmol) and diphenylacetylene (1.2 g, 7.0 mmol) in refluxing benzene (100 mL) for 12 h. After evaporation of the solvent under vacuum, the residue was chromatographed on silica gel with ethyl acetate1 petroleum ether (5195)as eluent which gave first ketone 9 (0.16 g, 12%) as a n oil and then complex 10 (0.67 g, 25%) as an orange solid: mp 143 "C; IH NMR (200 MHz, CDC13) 6 7.39 (m, 5H, ArH), 5.62 (d, l H , ArCr), 5.21 (t, 2H, ArCr), 5.04 (t, 2H, ArCr), 4.00 (m, l H , NCH), 3.27 (m, l H , NCH), 2.39 (m, lH), 2.07 (m, lH), 1.62 (m, 5H), 1.24 (m, 5H); NMR (50 MHz, CDC13) 6 232.85 (CO), 178.2 (CO), 130.11-127.40 (C=C, Ar),93.51-90.51 (ArCr), 58.52, 40.76, 37.92, 27.69, 23.01, 22.70, 20.72, 20.18 (CH2). MS for C27H27N04Cr. Calcd 481 (mlz). Found 481. Heating complex 10 in pyridine gave lactam 11 as a white solid: mp 126 "C; IR (CHC13) 1690 cm-'; IH NMR (200 MHz, CDC13) 6 7.24 (m, 8H, ArH), 6.82 (m, 2H, ArH), 4.03 (m, l H , NCH), 3.34 (m, l H , NCH), 2.13 (m, 5H), 1.45 (m, 10H); NMR (50 MHz, CDC13) 6 181.33 (CO), 140.22,137.72,133.89,129.24-126.51(C=C, Ar),60.49,40.56, 32.09,22.59,20.20, 19.71 (CH2), 12.24 (CH3). Anal. Calcd for C24H27NO: C, 83.47; H, 7.82; N, 4.06. Found: C, 83.32; H, 7.85; N, 3.90. Enamine 12 was obtained last (1g, 52%) as an oil: 'H NMR (200 MHz, CDC13) 6 7.68-7.23 (m, 10H, ArH), 6.84 (s, l H , =CHI, 3.86 (s, lH), 3.66 (s, l H , C=CHH), 3.24 (m, 4H, NCHZ),1.35 (m, 10H, CH2); 13CNMR (50 MHz, CDC13) 6 150.63 (N=C), 130.90, 129.44-126.82 (C=C, Ar), 80.52 (=CH2), 50.44 (NCH21, 27.51, 27.33, 26.04 (CHZ). MS for C23H27N. Calcd 317 (mlz). Found 317.

Parlier et al.

(CO)&r=C(H)N-CH&H&H&H2 (13b) was obtained from the corresponding formylamide and (C0)sCrNa~;yield 70%, yellow crystals: mp 51 "C; IR (CHC13) 2040,1970, 1920 cm-'; lH NMR (200 MHz, CDC13) 6 10.92 (s, l H , Cr=C(H)), 4.01 (m, 2H, NCHz), 3.74 (m, 2H, NCHd, 2.15 (m, 4H, 2CH2); 13C NMR (50 MHz, CDC13) 6 257.45 (Cr=C), 227.26, 217.85 (CO), 62.00, 55.58 (NCHz), 25.84, 25.44 (CH2). Anal. Calcd for C10H~N05Cr:C, 43.63; H, 3.27; N, 5.10. Found: C, 43.60; H, 3.32; N, 5.08. (CO)&r=C(Ph)NCH&H&H2CH2 (13c) was obtained from (CO)&r=(OEt)Ph and pyrrolidine; yield 80%, yellow crystals: mp 97 "C; IR (CHC13)2040,1940,1900 cm-l; lH NMR (200 MHz, CDC13) 6 7.2-6.6 (m, 5H, Ar),4.20 (m, 2H, NCHz), 3.15 (m, 2H, NCHz), 2.12 (m, 2H, CH2), 1.91 (m, 2H, CH2); NMR (100 MHz, CDCl3) 6 269.57 (Cr=C), 223.77,217.50 (CO), 153.87, 128.70, 125.72,118.39(Ar),59.39,55.81 (NCHz),25.37, 25.28 (CH2). Anal. Calcd for C I ~ H I ~ N O C, ~ C54.70; ~ : H, 3.70; N, 3.99. Found: C, 54.62; H, 3.62; N, 4.04. (CO)&~=C(SC&)(NCH~CHZCHZCH~) (13d) was obtained from (CO)&r=C(SC4H3)0Et and pyrrolidine in 80% yield as a yellow solid: mp 114 "C; 'H NMR (200 MHz, CDC13) 6 7.25 (m, 1 H, HC=C), 6.98 (m, l H , HC=C), 6.51 (m, l H , CH=C), 4.27 (m, 2H, NCH2) 3.50 (m, 2H, NCHz), 2.20 (m, 2H, CHz), 2.00 (m, 2H, CH2); 13C NMR (50 MHz, CDC13) 6 265.0 (Cr=C), 223.87, 217.35 (CO), 153.91, 127.13, 123.73, 117.73 (C=C), 59.95 (NCH),56.53 (NCH),25.56 (2 CH2). Anal. Calcd for C14H11N05SCr: C, 47.05; H, 3.08; N, 3.92. Found: C, 47.23; H, 3.08; N, 3.81. Pyrrole complex 14%pyrrole 15a, lactam complex 16% and lactam 17a were obtained upon refluxing complex 13a (R1 = Me) (2.89 g, 10 mmol) in benzene (100 mL) for 12 h in the presence of diphenylacetylene (1.8g, 10 mmol). Evaporation of the solvent under vacuum, followed by silica gel chromatography with petroleum etherlmethylene chloride (95/ 5) first gave pyrrole 15a (0.48 g, 17% as a white solid: mp 145 "C; IR (CHC13) 1600 cm-'; 'H NMR (200 MHz, CDC13) 6 7.28-7.07 (m, 10H, Ar),3.90 (m, 2H, NCHz), 2.88 (m, 2H, CH2), 2.27 (s, 3H, CH3), 2.03 (m, 2H, CH2), 1.82 (m, 2H, CH2); NMR (50 MHz, CDC13) 6 155.36, 137.24-118.47 (Ar),43.13 (NCHz), 23.75, 23.40, 21.12 (3CHz), 10.75 (CH3). MS for C21H21N+. Calcd 423. Found 423. Complex 14a followed (0.22 g, 5%)as yellow crystals: mp 145 "C; IR (CHC13) 1960, 1880 cm-'; IH NMR (200 MHz, CDC13) 6 7.30-7.00 (m, 5H, Ar), 5.34-5.15 (m, 5H, ArCr), 3.85 (m, 2H, NCHz), 2.96 (m, 2H, CHz), 2.14 (s, 3H, CH3), 2.01 (m, 2H, CH2), 1.88 (m, 2H, CH2); 13CNMR (50 MHz, CDC13) 6 233.99 (CO), 135.86-125.96 (Ar), 100.0, 95.0, 93.21, 90.16 (ArCr), 43.31 (NCHz), 23.97, 23.38, 21.02 (3 CH2). Anal. Calcd for C24H21N03Cr: C, 68.08; H, 4.96; N, 3.30. Found: C, 67.28; H, 4.93; N, 3.10. Lactam 17a was then obtained (0.17 g, 5.5%) as white crystals: mp 146 "C; IR (CHC13) 1730 cm-'; 'H NMR (200 MHz, CDC13) 6 7.276.84 (m, 10H, Ar), 3.64 (m, l H , NCH), 3.05 (m, lH, NCH), 2.50 (m, l H , CHI, 2.12 (s, 3H, CH3), 2.04 (m, l H , CHI, 1.88-1.63 (m, 4H, CHz); 13CNMR (50 MHz, CDC13) 6 189.93 (CO), 141.86, 137.81, 134.19,128.70-126.43, 122.21 (Ar,C=C), 64.67 (CPh), 42.77 (NCHz), 36.97,26.02,22.64 (3 CHz), 11.78 (CH3). HRMS for C21H21NO+. Calcd 303.1623. Found 303.1623. Finally complex 16a was obtained (1.145 g, 26%) as yellow crystals: mp 120 "C; IR (CHC13) 1980,1890, 1740 cm-l; IH NMR (200 MHz, C6Dd 6 7.18-6.77 (m, 5H, Ar),5.17 (d, l H , ArCr), 4.76 (d, l H , ArCr), 4.49 (m, l H , ArCr), 4.36 (m, l H , ArCr), 4.19 (m, l H , ArCr), 3.40 (m, l H , NCH), 2.54 (m, l H , NCH), 2.101.82 (m, 2H, CH2), 1.54 (s, 3H, CH3), 1.42-1.16 (m, 4H, CH2). MS for C24H21N0&r+. Calcd 439. Found 439. Treatment of complex 13a under the same conditions with diphenylacetylene, followed by evaporation of the solvent and treatment of the residue with pyridine a t reflux for 6 h, gave upon silica gel chromatography pyrrole 14a in 25% yield and lactam 17a in 19% yield. Pyrrole complex 14b, pyrrole 15b, lactam complex 16b, and lactam 17b were obtained under the same conditions as above. Silica gel chromatography of the residue of the reaction with petroleum etherlmethylene chloride as

Reaction of Aminocarbene-Chromium Complexes eluents gave, by collecting appropriate fractions (from 5/95 to 20/80), successively pyrrole 15b (0.30 g, 15%) as a white solid: mp 184 "C; 'H NMR (200 MHz, CDC13) 6 7.30-7.03 (m, 10H, Ar),6.72 (s, l H , C=CH), 4.02 (m, 2H, NCHz), 2.81 (m, 2H, CH2), 2.02 (m, 2H, CH2), 1.82 (m, 2H, CH2); 13C NMR (50 MHz, CDC13) 6 130.24-117.68 (Ar),45.62 (NCHd, 23.73,22.99, 21.34 (3 CH2). MS for CzoH1gN+. Calcd 273. Found 273. Complex 14b was then obtained (0.6 g, 19%) as yellow crystals: mp 175 "C; IR (CHC13) 1960, 1890, 1735 cm-l; 'H NMR (200 MHz, C & , ) 6 7.28-7.08 (5H, m, Ar),6.21 (s, l H , C=CH), 4.93 (d, J = 6.4 Hz, 2H), 4.51 (t,J = 6.4 Hz, 2H), 4.33 (t, J = 6.2 Hz, 2H) (ArCr), 3.13 (t, J = 6.2 Hz, 2H, NCHd, 2.78 (t, J = 6.2 Hz, 2H, C=C-CH2), 1.48 (m, 2H, CH2), 1.12 (m, 2H, CH2); I3C NMR (50 MHz, CDC13) 6 234.21 (CO), 138.0109.1 (Ar, C-C), 95.14, 92.92, 90.13 (ArCr), 45.30 (NCHz), 23.81,23.13, 21.12 (3CHz). Anal. Calcd for C23H~N03Cr:C, 67.48; H, 4.64; N, 3.42. Found: C, 67.34; H, 4.52; N, 3.32. Lactam 1% was obtained next (0.60 g, 20%) as a white solid: mp 148 "C; IR (CHC13) 1735 cm-'; IH NMR (200 MHz, CsDd 6 7.28-6.83 (m, 10H, Ar), 6.48 (s, l H , C-CHI, 3.47 (m, l H , NCH), 2.26 (m, lH), 2.11-1.97 (m, 3H) (ArCr), 1.36-1.24 (m, 3H); I3C NMR (50 MHz, CDC13) 6 188.02 (CO), 138.241, 135.89, 133.44, 128.49-124.73 (Ar,C=C), 63.53 (CPh), 45.58 (NCHd, 35.87, 26.79, 22.60 (3 CH2). Anal. Calcd for CzoH19NO: C, 83.04; H, 6.57; N, 4.84. Found: C, 83.09; H, 6.65; N, 4.80. Lactam complex 16b was obtained last (0.60 g, 20%) as a n oil; IR (CHC13) 1970, 1900, 1735 cm-l; 'H NMR (200 MHz, C6D6) 6 7.35-6.90 (m, 5H, h), 6.1 (s, 1H, CH=C), 5.25 (d, l H , ArCr), 4.90 (d, l H , ArCr), 4.35 (t, l H , ArCr), t l H , ArCr), 4.05 (t, lH,ArCr), 3.55 (m, l H , NCH), 2.35-1.65 (m, 4H), (m, l H , NCH), 1.6-1.18 (m, 6H, 3CH2). MS for C23H19N04Cr+. Calcd 425. Found 425. Pyrrole 15c, lactam 17c, and lactam complex 16c were obtained from complex IC (3 g, 8.54 mmol) and diphenylacetylene (1.5 g, 8.6 mmol) as above. Appropriate fractions were collected to give first with petroleum ethedmethylene chloride (70/30) a mixture of pyrrole complex 14c and pyrrole 15c, which was refluxed in pyridine to give after filtration through silica gel pyrrole 15c as a white solid (0.40 g, 14%): mp 194 "C; IR (CHC13) 1600 cm-'; 'H NMR (200 MHz, CDC13) 6 7.286.88 (m, 15H Ar),3.88 (m, 2H, NCHz), 2.94 (m, 2H, CHd, 1.91 (m, 4H, 2 CH2); I3C NMR (50 MHz, CDC13) 6 136.04-119.21 (C=C, Ar),44.75 (NCH2),23.93, 23.49, 21.21 ( 3 CH2). Anal. Calcd for Cz6H23N: C, 89.36; H, 6.63; N, 4.00. Found: C, 89.27; H, 6.67; N, 3.89. Elution with the same mixture of solvents then gave complex 16c (2.25 g, 42%) as yellow crystals: mp 177 "C; IR (CHC13) 1980,1895,1740cm-'; IH NMR (200 MHz, CDC13) 6 7.32-6.93 (m, 10H, Ar),5.46 (d, l H , ArCr), 5.28 (d, 2H, ArCr), 5.06 (t, l H , ArCr), 4.93 (t, l H , ArCr), 3.60 (m, l H , NCH), 2.85-2.65 (m, l H , NCH), 2.25-1.65 (m, 6H, 3 CH2); I3C NMR (50 MHz, CDC13) 6 232.86 (CrCO), 186.43 (CO), 146.04, 134.20-121.20 (Ar,C=C), 107.20, 94.67, 94.31, 89.17 (ArCr), 62.34 (CPh), 44.81 (NC), 43.06, 39.32, 25.94, 22.83 (4 CH2). Anal. Calcd for C2gH23N04Cr: C, 69.46; H, 4.59; N, 2.79. Found: C, 69.30; H, 4.45; N, 2.71. Lactam 17c was then obtained (0.45 g, 16%)as a white solid: mp 185 "C; IR (CHC13) 1740 cm-'; IH NMR (200 MHz, CDC13) 6 7.44-6.93 (m, 15H, Ar), 3.64-3.54(m,lH,NCH), 2.64-2.76 (m,lH,NCH),2.331.75 (m, 6H, 3 CH2); I3C NMR (50 MHz, CDC13) 6 189.75 (CO), 145.99, 137.33-122.49 (Ar,C=C), 65.93 (CPh), 44.11 (NCHd, 37.94, 26.21, 22.58 (3 CH2). HRMS for C26H23NO+. Calcd 365.1779. Found 365.1781. Pyrrole 15d and Lactam 17d. A solution of complex Id (1.815 g, 5.08 mmol) in benzene (50 mL) was refluxed for 12 h in the presence of diphenylacetylene (1g, 5.6 mmol). Evaporation of the solvent followed by silica gel chromatography with petroleum ethedmethylene chloride (80/20) first gave a yellow oil, which was not further purified. Treatment in boiling pyridine for 6 h gave, after evaporation of the solvent and filtration through silica gel, pyrrole 16d as a white solid (0.8 g, 44%): mp 172 "C; IH NMR (200 MHz, CDC13) 6 7.29-6.91 (m, 13H, Ar), 3.93 (m, 2H, NCHz), 2.91 (m, 2H, CHd, 1.98 (m, 2H, CHz), 1.86 (m, 2H, CHZ); 13C NMR (50 MHz, CDC13) 6

Organometallics, Vol. 14, No. 6, 1995 2771 135.77-119.61 (15 peaks, Ar), 44.54 (NCHz), 23.81, 23.52; 21.06 (3 CH2). Anal. Calcd for C24H21NS: C, 81.12; H, 5.91; N, 3.94. Found: C, 81.18; H, 5.98; N, 3.79. Then petroleum ethedmethylene chloride (50/50) eluted a second fraction, which was also treated with pyridine to give, after filtration through silica gel, lactam 17d (0.86 g, 45.6%) as a white solid: mp 242 "C; lH NMR (200 MHz, CDC13) 6 7.28-6.90 (m, 13H, Ar), 3.71-3.61 (m, l H , NCH), 3.18-3.10 (m, l H , NCH), 2.72-2.64 (m, l H , CHI, 2.26-2.13 (m, 2H, CHd, 1.96-1.83 (m, 3H, CH2); 13C NMR (100 MHz, CDC13) 6 189.81 (CO), 139.74, 136.91, 133.41, 128.86-126.87 (Ar),65.73 (CPh), 45.03 (NCHz), 37.22, 25.97, 22.41 (3 CH2). Anal. Calcd for NOS: C, 77.62; H, 5.66; N, 3.77. Found: C, 77.02; H, 5.57; N, 3.60. Lactam complex 19 and lactam 20 were obtained upon heating of complex 13c (1.5 g, 4.27 mmol) in refluxing benzene in the presence of 1-phenyl-1-propyne(1mL, 8 mmol) as above. Silica gel chromatography of the residue with petroleum ether/ ethyl acetate (80/20) first gave complex 19c (0.7 g, 38%) as orange crystals: mp 164 "C; IR (CHC13) 1980,1890,1740 cm-l; IH NMR (200 MHz, CDC13) 6 7.54-7.28 (m, 5H, Ar), 5.515.22 (m, 5H, ArCr), 3.49 (m, l H , NCH), 2.71 (m, l H , NCH), 2.23 (m, lH), 2.01 (m, 2H), 1.86 (s, 3H, CH3); I3C NMR (50 MHz, CDC13) 6 190.91 (CO), 145.17, 137.71, 131.78, 128.83127.19, 119.41 ( C 4 , Ar), 65.03 (CPh), 39.25 (NCHz), 25.61, 22.87 (CHz), 10.35 (CH3). Anal. Calcd for C24H21N04Cr: C, 65.60; H, 4.55; N, 3.19. Found: C, 65.68; H: 4.65; N, 3.24. Heating complex 19c in pyridine for 6 h gave after silica gel chromatography lactam 20 (0.3 g, 61%) as a white solid: mp 113 "C; IR (CHC13) 1740 cm-'; 'H NMR (50 MHz, CDC13) 6 7.58-7.27 (m, 10H, Ar), 3.55 (m, l H , NCH), 2.75 (m, l H , NCH), 2.38 (m, l H , CH), 2.02 (m, lH), 1.72 (m,3H), 1.58 (s, 3H, CH3). Anal. Calcd for C Z ~ H ~ I N O C,: 83.16; H, 6.93; N, 4.62. Found: C, 82.85; H, 6.99; N, 4.52. (CO)&r=C(H)N(CBHld)(21) was obtained from formylperhydroindole and (CO)&rNaz as a yellow solid: mp 40 "C; IR (CHC13)2020,1970,1925 cm-l; 'H NMR (200 MHz, CDC13) 6 10.93, 10.80, 10.71, 10.70 (s, l H , Cr=C(H) for the four isomers), 4.23 (m, l H , NCH), 3.96 (m, l H , NCH), 3.55 (m, l H , NCH), 2.45 (m, l H , CHI, 2.10-1.0 (m, 10H, CHd; 13C NMR (50 MHz, CDC13) 6 253.9 (Cr=C), 224.0, 218.1 (CO), 66.52, 59.02 (NCH2, NCH), 37.21 (CHI, 26.76, 25.49, 23.55, 19.90 (CH2). Anal. Calcd for C14H1~jN05Cr: C, 51.06; H, 4.56; N, 4.25. Found: C, 51.42; H, 4.61; N, 4.11. Pyrrole 22 and pyrrole complex 23 were obtained as above from complex 21 (3.5 g, 8.5 mmol) and diphenylacetylene (2 g, 11mmol). Chromatography of the residue with petroleum ethedethyl acetate (95/5) first gave compound 22 (0.9 g, 20%) as a white solid: mp 148 "C; 'H NMR (200 MHz, CDC13) 6 7.32-6.72 (m, 10H, Ar), 6.69 (s, l H , C=CH), 4.16-3.90 (m, 2H, NCHz), 3.10 (m, l H , =CCH), 2.34 (m, lH), 2.17 (m, l H ) , 1.71-1.04 (m, 9H); 13CNMR (50 MHz, CDC13) 6 130.45-116.95 (C=C, Ar), 45.72 (NCHz), 34.0 (CHI, 32.45 (CHI, 31.53, 28.64, 25.89, 24.41, 21.07 (5 CH2). HRMS for C24H25N MT. Calcd 327.1986. Found 327.1990. Elution with the same solvents gave complex 23 (0.4 g, 11%) as a yellow solid: mp 170.1 "C; IR (CHC13) 1965, 1885 cm-l; 'H NMR (200 MHz, CDC13) 6 7.33-7.21 (m, 5H, Ar), 6.83 (s, l H , CH=C), 5.36-5.08 (m, 5H, ArCr), 4.07-3.93 (m, 2H, NCHz), 2.94 (m, l H , C-CCH), 2.341.20 (m, 11H). MS for C27H25N03Cr (M+). Calcd 463. Found 463. (CO)&r=C(Me)NCH#H2SCH2 (24a) was obtained from (CO)sCr=C(Me)OEt and thiazolidine in 65% yield as a yellow solid. Silica gel chromatography with petroleum ethedmethylene chloride (98/2) first gave 24a-E as yellow crystals (368): mp 101 "C; 'H NMR (200 MHz, CDC13) 6 4.60 (s, 2H, NCHzS), 4.56 (m, 2H, NCHz), 3.18 (m, 2H, SCHz), 2.77 ( s , 3H, CH3); I3C NMR (100 MHz, CDC13) 6 274.63 (Cr=C), 223.03, 217.52 (CO), 63.32 (NCHzS), 52.82 (CH2N),41.43 (CHzS),29.06 (CH3). Compound 24a-Z was then obtained as yellow crystals: mp 103 "C; 'H NMR (200 MHz, CDC13) 6 5.19 (s, 2H, NCHzS), 3.86 (m, 2H, NCHz), 3.25 (m, 2H, SCHd, 2.76 (s, 3H, CH,); I3C NMR (100 MHz, CDC13) 6 274.15 (Cr=C), 223.11,

2772 Organometallics, Vol. 14,No. 6,1995

Parlier et al.

(NCH2). Anal. Calcd for Cl4HgN05Cr: C, 47.32; H, 2.53; N, 217.55 (CO), 61.86 (NCHsS), 54.24 (CH2N),41.96 (CH2S), 30.83 3.94. Found: C. 47.12; H, 2.61; N, 4.03. (CH3). Anal. Calcd for CloHgN05Cr: C, 39.08; H, 2.93; N, Lactam 32a and pyrrole 31a were obtained upon heating 4.56. Found: C, 39.02; H, 2.92; N, 4.56. a mixture of complex 30a (2.5 g, 7.16 mmol) and diphenyl(CO)5C~C(Ph)NCH2SCH2CH2 (24b) was obtained from acetylene (2.55 g, 14.0 mmol) in benzene as above. Silica gel (CO)&r=C(Ph)OEt and thiazolidine in 66% yield as a yellow chromatography of the residue of the reaction with petroleum solid (60/40 EIZ mixture): mp 115 "C; 'H NMR (200 MHz, ethedmethylene chloride (90/10) as the eluent first gave CDC13)6 (llb-2)7.43-6.72 (m, 5H, Ar), 5.32 (s, 2H, NCHzS), pyrrole 31a (0.045 g, 1.8%) as a white solid: mp 174 "C 3.56 (m, 2H, NCHz), 3.06 (m, 2H, CH2); (llb-E)7.43-6.72 (m, (decomp); 'H NMR (200 MHz, CDC13) 6 7.39-6.81 (m, 15H, 5H, Ar), 4.64 (m, 2H, NCHz), 4.24 (m, 2H, NCHzS), 3.29 (m, Ar), 5.63 (m, l H , CH=C), 5.38 (m, l H , CH=C), 3.95 (m, 2H, NMR (100 MHz, CDC13) 6 275.72 (CFC), 223.07, 2H, CH2); NCHz), 3.32 (m, 2H, CH2). HRMS for C~&IN+. Calcd 216.95 (CO), 153.20, 128.91, 126.37, 118.25 (Ar), 61.48, 61.30, 56.10,56.02,42.25,29.68 (CHz). HRMS for C ~ S H ~ ~ N O (M+ ~ S C ~ 347.1673. Found 347.1673. Elution with petroleum ether/ ethyl acetate (80/20) gave lactam 32a (1.6 g, 61.5%) as a white - CO). Calcd 340.9813. Found 340.9814. solid: mp 89-90 "C; 'H NMR (200 MHz, CDC13) 6 7.47-6.66 Pyrrole 25a was obtained upon heating a mixture of (m, 15H, Ar), 5.87 (m, l H , CH=C), 5.69 (m, l H , CH=C), 4.65 complex 24a (3.5 g, 11.4 mmol) and diphenylacetylene (2.5 g, (m, l H , NCH), 3.30 (m, l H , NCH), 3.06 (m, l H , HCH), 2.46 14 mmol) as above. Silica gel chromatography first gave with (m, l H , HCH); 13C NMR (50 MHz, CDC13) 6 168.15 (CO), petroleum ethedethyl acetate (97/3) pyrrole 25 (0.76 g, 22%) 158.52, 138.14, 132.87, 131.17, 129.44-126.67, 124.85, 122.06 and then a fraction of complexed and uncomplexed products (Ar, C-C), 66.08 (NC), 38.16 (NCHz), 31.12 (CH2). Anal. (1.6 g), which was treated with pyridine. The residue of this Calcd for C26HzlNO: C, 85.95; H, 3.85; N, 5.78. Found: C, reaction was then chromatographed on silica gel. Elution with 85.40; H, 3.77; N, 6.03. petroleum ethedethyl acetate (95/5) first gave pyrrole 25 (0.125 Lactam 32b and pyrrole 31b were obtained from complex g), total yield 25.596, as a white solid, unstable in solution: 30b (1.77 g, 4.9 mmol) and diphenylacetylene (1g, 5.6 mmol) mp 74 "C; IR (CHC13) 1600 cm-l; 'H NMR (200 MHz, CDC13) as above. Treatment of the residue of the reaction with 6 7.27-7.01 (m, 10H, Ar), 4.12 (m, 2H, NCHz), 3.90 (9, 2H, pyridine for 6 h followed by silica gel chromatography with NMR (50 NCHzS), 3.11 (m, 2H, CHz), 2.25 (s, 3H, CH3); petroleum ethedmethylene chloride (90/10) first gave pyrrole MHz, CDC13) 6 135.88-119.69 (Ar), 44.28 (NCHz), 27.50 (CHz), 31b (0.025 g); 'H NMR (200 MHz, CDC13) 6 7.33-6.91 (m, 13H, 24.61 (CHz), 10.31 (CH3). HRMS C ~ O H I ~ N (M+). S Calcd Ar), 6.31 (m, 2H, CH=CH), 3.98 (m, 2H, CH2), 2.92 (m, 2H, 305.1238. Found 305.1239. After elution with with petroleum CHz). Elution with petroleum ether/ethyl acetate (90/10) gave ethedethyl acetate (90/10) ketone 9 was obtained as a n oil (0.22 lactam 32b (0.8 g, 43.5%) as a white solid: mp 137 "C; 'H NMR g, 8.5%), in all respects identical with a n authentic sample. (200 MHz, CDC13) 6 7.45-6.79 (m, 15H, Ar), 5.81 (m, 2H, Furan 26 and amido ketone 27 were obtained upon CH=CH), 4.66 (m, l H , NCH), 3.54 (m, l H , NCH), 2.95 (m, heating a mixture of complex 24b (2.5 g, 6.77 mmol) and l H , HCH), 2.55 (m, l H , HCH); I3C NMR (100 MHz, CDC13) 6 diphenylacetylene (2.35 g, 13.2 mmol) in benzene as above. 167.74 (CO), 158.14, 142.23, 132.70-121.78 (Ar, CH=CH), Silica gel chromatography of the residue of the reaction with 64.49 (NC), 38.26 (NCHz), 33.60 (CH2). Anal. Calcd for petroleum ethedethyl acetate (95/5) as eluent gave the CrC24H19NOS: C, 78.04; H, 5.15; N, 3.79. Found: C, 77.67; H, (CO)3complex of 26 followed by indenone 28 (0.13 g, 7%) and 5.14; N, 3.85. indanone 29 (0.20g, ll%), the spectroscopic data of which were (CO)&r=C(H)N(CH2)3 (33a) was obtained from formylidentical in all respects with those of previously synthesized azetidine and (CO)&rNaz as a yellow solid in 93% yield: mp samples. Treatment of the complex of the aminofuran in 61 "C; IR (CHC13) 2040,1970,1920 cm-'; 'H NMR (400 MHz, boiling pyridine for 6 h followed by evaporation of the solvent CDC13) 6 10.36 (s, l H , Cr=C(H)), 4.60 (t, J = 7.5 Hz, 2H, and chromatography of the residue first gave with petroleum NCHz),4.28 (t,J = 7.5 Hz, 2H, NCHd, 2.41 (m, 2H, CHZ);I3C ethedethyl acetate (95/5) the aminofuran 26 (1.1g, 42%) as a NMR (100 MHz, CDC13) 6 255.30 (CFO), 223.65,217.58 (CO), white solid: mp 108 "C; 'H NMR (200 MHz, CDCl3) 6 7.2861.43, 58.43 (NCHz),13.59 (CHz). Anal. Calcd for CgH7N057.16 (m, 15H, Ar),4.35 (s, 2H, NCHzS), 3.62 (m, 2H, NCHz), Cr: C, 41.14; H, 2.68; N, 5.36. Found: C, 41.19; H, 2.74; N, NMR (50 MHz, CDC13) 6 151.34 (NCO), 3.13(m, 2H, CH2); 5.33. 141.52 (C-01, 133.84-109.56 (Ar, C=C), 56.16, 54.40, 32.0 (CO)&r=C(Me)NCH&H&H2 (33b) was obtained from (CH2). HRMS CzsHzlNOS (M+). Calcd 383.1343. Found (CO)&r=C(Me)OEt and azetidine in 91% yield as a yellow 383.1342. Amido ketone 27 (0.2 g, 7%) was then obtained as solid: mp 31 "C; IR (CHC13) 2040, 1970,1920 cm-'; 'H NMR a 50/50 mixture of two isomers; white solid: mp 195 "C; IR (200 MHz, C6&) 6 3.88 (m, 2H, NCHZ),2.66 (m, 2H, NCHz), (CHC13) 1630,1658 cm-'; 'H NMR (200 MHz, CDC13) 6 7.891.75 (s, 3H, CH3), 1.06 (m, 2H, CHZ);13CNMR (50 MHz, CDC13) 7.12 (m, 15H, Ar), 4.46 (s, 2H, NCHzS), 3.70 (m, 2H, NCHZ), 6 264.23 (Cr=C), 223.01, 218.23 (CO), 59.56 (NCHz), 55.82 2.92 (m, 2H, SCHz); 13CNMR (100 MHz, CDC13) 6 197.04 (CO), (NCHz),35.53 (CHz), 13.44 (CH3). Anal. Calcd for C10HgN05168.07 (CO), 140.08-128.42 (Ar, C=C), 50.25 and 49.28,48.22 Cr: C, 43.63; H, 3.27; N, 5.09. Found: C, 43.69; H, 3.32; N, and 47.63, 30.71 and 29.83 (CHz). HRMS for C Z ~ H ~ I N O Z S 4.82. (M+). Calcd 399.1329. Found 399.133. (CO)&FC(P~)NCH~CH~CHZ (33c) was obtained from (CO)&r=C(Ph)N(CH&H=CHCH2) (30a) was obtained (CO)&r=C(Ph)OEt and azetidine in 91% yield as yellow from (CO)&(Ph)OEt and pyrroline as a yellow solid in 97% crystals: mp 124-126 "C; IR (CHC13) 2040, 1940 cm-'; 'H yield: mp 110 "C; 'H NMR (200 MHz, CDCl3) 6 7.40 (m, 2H, NMR (200 MHz, CDC13) 6 7.37, 7.23, 6.78 (m, 5H, Ar), 4.84 Ar), 7.17 (m, l H , Ar), 6.75 (m, 2H, Ar), 6.07 (m, l H , CH-C), (m, 2H, NCHz), 3.91 (m, 2H, NCHz), 2.36 (m, 2H, CH2); 13C 5.79 (m, l H , CH=C), 5.02 (m, 2H, NCHz), 3.97 (m, 2H, NCHz); NMR (50 MHz, CDC13)6 266.76 (Cr=C), 223.50, 217.56 (CO), I3C NMR (50 MHz, CDC13) 6 273.94 (Cr=C), 223.70, 217.51 149.87, 128.71, 126.64, 119.60 (Ar), 59.89 (NCHz), 57.38 (CO), 154.02, 129.05, 126.09, 125.12, 118.31 (Ar, C=C), 64.88 ~ C53.41; T: (NCH2), 13.79 (CH2). Anal. Calcd for C ~ ~ H I ~ N O C, (NC), 61.05 (NC). Anal. Calcd for C16HllN05Cr: C, 55.00; H, 3.26; N, 4.15. Found: C, 52.89; H, 3.24; N, 3.86. MS for H, 3.15; N, 4.01. Found: C, 55.05; H, 3.12; N, 3.87. C I ~ H ~ ~ N O Calcd ~C~+ 337. . Found 337. (C~)~C~=C(C~HSS)N(CH~CH=CHCH~) (30b) was ob(CO)&r=C(Me)NCH&H(Ph)CH2 (33d) was obtained tained from (C0)5CrC=(C4H3S)OEtand pyrroline as a yellow from (CO)&r=C(Me)OEt and 3-phenylazetidine in 94% yield solid in 88% yield: mp 62 "C; 'H NMR (200 MHz, CDC13) 6 as a yellow solid: mp 59-61 "C; IR (CHC13) 2040, 1920 cm-I; 7.28 (m, l H , thienyl), 6.99 (m, l H , thienyl), 6.50 (m, l H , lH NMR (200 MHz, CDC13)6 7.41-7.25 (m, 5H, Ar), 5.07 (m, l H , NCH), 4.72 (m, 2H, NCHz), 4.33 (m, l H , NCH), 4.01 (m, thienyl), 6.07 (m, l H , CH=C), 5.83 (m, l H , CH=C), 5.03 (m, NMR (50 MHz, CDC13) 6 2H, NCHz), 4.23 (m, 2H, NCH2); I3C NMR (50 MHz, CDC13) 6 l H , CHPh), 2.50 (9, 3H, CH3); 266.74 (Cr=C), 222.98, 218.25 (CO), 140.37, 129.28, 127.84, 269.91 (Cr=C), 223.59, 217.16 (CO), 153.60, 127.19, 125.94, 126.65 (Ar), 66.50 (NCHz), 62.91 (NCHz), 36.02 (CHI, 31.59 125.06, 123.81, 117.38 (thienyl, C=C), 65.25 (NCHz), 61.04



Table 11. Crystal Data for Compounds 3, 14a, 18,22, and 24a C27H250N (3)

C24H2103NCr (14a)

C1gH1205Cr (18)

C24H25N (22)

CloH905NSCr (24a)

423.43 triclinic P-1 6.918(1) 10.057(1) 15.193(2) 72.410(9)

372.3 orthorhombic Pc2lb 10.356(1) 12.366(5) 12.529(2)

327.47 monoclinic P2 lln 11.119(3) 10.682(2) 15.428(3)

275.18 monoclinic

A

379.5 monoclinic P21ln 10.080(4) 11.727(3) 18.014(6)

A deg

102.40(3)

84.99(1) 84.66(3)

2080(14) 4 1.21 0.68

lOOl(3) 2 1.40 5.80

1604.4(8) 4 1.54 7.20

CAD4 graphite Mo Ka w12e 0.8 0.34 tan 6 3-50 3648 1327

CAD4 graphite Mo Ka 012e 1.2 0.34 tan 6 3-60 5820 3647

CAD4 graphite Mo Ka 012e 0.8 0.34 tan 0 2-50 1486 1089

0.065 0.063 DIFABS 0.9011.10 0.70 10-4 unit wt 180

0.037 0.037 DIFABS 0.8311.16 no unit wt 238

0.029 0.029 DIFABS 0.8111.12 no unit wt 264

compd cryst params fw cryst syst space group a,A b, A C,

a,deg Y > deg

v, A3

z e, g cm-3

p(Mo Ka),cm-' data collection diffractometer monochromator radiation scan type scan range q, deg 20 range, deg no. of reflns collected no. of reflns used (I > 3d1)) refinement R RW*

abs. con-.** midmax abs second exinct param weighting scheme 1s params

+

+

(CH3). Anal. Calcd for C1&3NO&r: C, 54.70; H, 3.70; N, 3.98. Found: C, 54.98; H, 3.74; N, 3.85. (CO)&rC(H)N-CH&H(Ph)CH2 (33e) was obtained and (C0)sCrNaz as a yellow from 1-formyl-3-phenylazetidine solid in 50% yield: mp 50 "C; IR (CHC13) 2050, 1975, 1915 cm-l; 'H NMR (200 MHz, CDC13) 6 10.61 (s, l H , Cr=C(H)), 7.40 (m, 5H, Ar),5.05 (m, l H , NCH), 4.68 (m, 2H, NCHz), 4.44 (m, l H , NCH), 4.02 (m, l H , CHPh); I3C NMR (50 MHz, CDC13) 6 257.63 ( C r C ) , 223.6, 217.56, (CO), 139.98, 129.19, 127.61, 68.26, 65.20 (NCHz), 31.83 (CHPh). Anal. Calcd 126.55 (Ar), for C15HllN05Cr: C, 53.41; H, 3.26; N, 4.15. Found: C, 53.41; H, 3.26; N, 4.13. Lactam 35a was obtained upon heating complex 33a (2.0 g, 7.6 mmol) in benzene in the presence of diphenylacetylene (1.5 g, 8.4 mmol) followed by silica gel chromatography. Elution with petroleum ethedethyl acetate (80/20) gave lactam 35a (0.63 g, 30%) as a white solid: mp 141 "C; IR (CHC13) 1655, 1600 cm-l; 'H NMR (200 MHz, CDC4) 6 7.39 (m, 10H, Ar),4.67 (m, 1H, NCH), 3.64 (m, l H , NCH), 3.40 (m, l H , NCH), 2.36 (m, 3H), 1.41 (m, 1H);I3C NMR (100 MHz, CDC13) 6 174.69(CO), 153.86,133.26, 131.88-129.49 (C=C,Ar), 66.77 (NC), 42.49 (NCHd, 29.98, 28.94 (2 CH2). HRMS for C19H17ON+. Calcd 275.1310. Found 275.1310. Lactam 35b was obtained in 40% yield from complex 33b as a white solid: mp 137 "C; IR (CHC13) 1675 cm-l; 'H NMR (200 MHz, CDC13) 6 7.37 (m, 10H, Ar),3.77 (m, lH, NCH), 3.37 (m, l H , NCH), 2.46 (m, 2H), 2.20 (m, lH), 1.88 (m, lH), 1.20 (s, 3H, CH3); 13C NMR (50 MHz, CDC13) 6 173.70 (CO), 159.21-127.83 (C=C, Ar),72.22 (C-N), 41.34 (NCHz), 35.15, 28.40, 22.24 (CHz, CH3). Anal. Calcd for CzoH1gNO: C, 83.04; H, 6.57; N, 4.84. Found: C, 82.53; H, 6.48; N, 4.54. MS for CzoH19NO+. Calcd 289. Found 289. Pyrrole 34c and lactam 35c were obtained from complex 33c (2.6 g, 7.71 mmol) and diphenylacetylene (2.85 g, 16 mmol) in benzene as above. Treatment of the residue of the reaction with pyridine under reflux for 6 h gave first, after silica gel chromatography with petroleum etherlmethylene chloride (901 lo), pyrrole 34c (0.047 g, 1.8%) as a white solid: mp 218 "C; IH NMR (200 MHz, CDC13) 6 7.25-7.00 (m, 15H, Ar), 4.08

+

p211n

8.3011(9) 11.949(1) 13.101(2)

102.23(2)

95.74(1)

1791(7)

1293(1)

4 1.21 0.65

4 1.41 8.69

CAD4 graphite Mo Ka 0128 1.2 0.34 tan 0 2-50 3159 1488 0.036 0.034 DIFABS 0.8711.13 no unit wt 303

CAD4 graphite Mo Ka w12e 1.2 0.34 tan 0 3-56 3103 2137 0.036 0.035 DIFABS 0.89l1.12 93 x 10-6 unit wt 193

+

+

(m, 2H, NCHz), 3.11 (m, 2H, CH2), 2.56 (m, 2H, CH2); I3C NMR (50 MHz, CDC13) 6 136.17-124.90 (Ar), 46.49 (NCHz), 27.23 (CHz), 24.99 (CH2). HRMS for C25HzlN+. Calcd 335.1674. Found 335.1674. Eluting with petroleum ethedethyl acetate (80/20), lactam 35c was then obtained (0.65 g, 24%) as a white solid: mp 119 "C; IR (CHC13) 1680 cm-'; 'H NMR (200 MHz, CDC13) 6 7.38-6.90 (m, 15H, Ar),3.82 (m, l H , NCH), 3.33 (m, l H , NCH), 2.80 (m, lH), 2.37 (m, lH), 2.04 (m, 2H); I3C NMR (50 MHz, CDC13) 6 174.13 (CO), 159.62, 139.12, 133.87, 131.21-126.22 (C=C, Ar), 78.19 (NC), 41.46 (NCHz), 34.75 (CHz), 28.49 (CH2). Anal. Calcd for C2bH21NO: C, 85.47; H, 5.98; N, 3.98. Found: C, 85.65; H, 5.93; N, 3.71. Lactam 35d was obtained from complex 33d (2 g, 5.6 mmol) and diphenylacetylene (1.5 g, 8.4 mmol) as above in 43% yield as a mixture of two isomers, which were separated by silica gel chromatography with petroleum ethedethyl acetate (80/ 20) as eluent. First isomer (41%), white solid: mp 219 "C; IR (CHC13) 1670 cm-'; 'H NMR (200 MHz, CDC13) 6 7.28 (m, 15H, Ar), 4.45 (m, l H , CHPh), 3.58 (m, lH, NCH), 3.28 (m, l H , NCH), 2.94 (m, IH, CCH), 2.14 (m, l H , CCH), 1.48 ( s , 3H, CH3); '3C NMR (50 MHz, CDC13) 6 174.70 (CO), 159.64,141.45, 133.62, 131.55-127.03 ( ' 2 4 , Ar),71.75 (C-N), 49.44 (NCHz), 47.94 (CPh), 42.73 (CH2),28.56 (CH3). Anal. Calcd for C26H23NO: C, 85.47; H, 6.30; N, 3.83. Found: C, 85.74; H, 6.21; N, 3.68. Second isomer (in trace amounts): mp 64 "C; lH NMR (200 MHz, CDC13) 6 7.27 (m, 15H, Ar),4.08 (m, lH, CHPh), 3.82 (m, 2H, NCHz), 2.60 (m, lH), 2.02 (m, lH), 1.37 (s, 3H, CHS); '3C NMR (50 MHz, CDC13) 6 173.81 (CO), 159.33, 141.84, 133.76-127.17 (C=C, Ar), 72.89 (NC), 49.21 (NCH2), 48.67 (CPh), 44.90 (CH2), 22.62 (CH3). MS for C2&3NO+. Calcd 365. Found 365. (CO)&r=C(Me)N(C&hz) (36) was obtained from the corresponding substituted azetidine and (CO)&r=-C(Me)OEt in 73% yield as yellow crystals: mp 93-95 "C; IR (CHC13) 2040, 1920 cm-'; 'H NMR (200 MHz, CDC13) 6 4.56 (m, l H , NCH), 4.42 (m, l H , NCH), 4.14 (m, 1H, NCH), 2.54 (m, 1H), 2.49 (s, 3H, CH3), 2.41 (m, 2H), 1.78 (m, lH), 1.53 (m, 3H), 1.15 (m, 2H); '3C NMR (50 MHz, CDC13) 6 265.10 (CFC), 223.1,218.48 (CO), 75.35 (NCH), 62.71 (NCHz), 39.95, 38.11, 33.98, 31.27,

Parlier et al.

2774 Organometallics, Vol. 14, No. 6, 1995 27.20,23.67. Anal. Calcd for C15H15N05Cr: C, 52.78; H, 4.35; N, 3.98. Found: C, 52.61; N, 4.35; N, 3.98. MS for C15H15N O & - + . Calcd 341. Found 341. Lactam complex 37 was obtained from complex 36 (1 g, 2.91 mmol) and diphenylacetylene (0.8 g, 4.49 mmol) as above after silica chromatography with petroleum ethedmethylene chloride as eluent (65/35) a s a yellow solid (0.65 g, 45%): mp 87 "C; IR (CHC13)1970,1900,1670 cm-'; IH NMR (200 MHz, CDC13) 6 7.35-7.24 (m, 5H, Ar), 6.01, 5.46, 5.25,4.90 (m, 5H, ArCr), 4.08 (m, l H , NCH), 3.61 (m, lH), 2.77-2.28 (m, 4H), 1.85 (s, 3H, CH3), 1.63-1.08 (m, 6H); 13C NMR (50 MHz, CDC13) 6 232.22 (CO), 167.48 (CO), 130.00, 129.64, 128.82, 128.30 (Ar), 97.75,95.68,94.52,89.50,88.63 (ArCr), 71.50 (NC), 55.76,44.84,43.41,40.82,40.04,35.80,29.75,28.51,22.50 (4 CH, 4 CH2, CH3). HRMS for C28HzsN04Cr (M+ - 2 CO). Calcd 435.1290. Found 435.1291. X-ray Studies. Intensity data were collected a t room temperature on a Nonius CAD4 diffractometer using graphitemonochromated Mo K a radiation. Crystal data and data collection parameters are listed in Table 11. For each compound, the accurate cell dimensions and orientation matrix were obtained from least-squares refinements of the setting angles of 25 well-defined reflections. No decay in the intensities of two standard reflections was observed during the course of data collections. The usual corrections for Lorentz and polarization effects were applied. Computations were performed by using CRYSTAL adapted on a Microvax-I1 computer.18 Scattering factors and correc-

tions for anomalous dispersion were from ref 19. The structures were solved by using direct method (SHELXSIZ0for compounds 3,22, and 24a and by standard Patterson-Fourier techniques for compounds 14a and 18. Absorption corrections were applied (DIFABS). For 3, non-hydrogen atoms were refined anisotropically except for the C atoms of the phenyl rings, which were left. isotropic. For all other compounds all non-hydrogen atoms were refined anisotropically, hydrogen atoms were located on difference-Fourier maps, and their coordinates were refined with an overall refinable isotropic thermal parameter. In Tables 1-5 are listed main bond lengths and angles for the five compounds.

Acknowledgment is made to Centre National de la Recherche Scientifique and to Commission of the European Communities (DGSRD, International Scientific Cooperation) for financial support. Supplementary Material Available: Complete tables of atomic coordinates, anisotropic thermal parameters, bond lengths and angles (Tables Sl-Sl5) (18 pages). This material is contained in many libraries on microfiche, immediately follows this article in the microfilm version of the journal, and can be ordered from the ACS; see any current masthead page for ordering information. OM940582R

Reaction of Aminocarbene Complexes of Chromium with Alkynes. 5

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