Enyne Metathesis Using Chromium Carbene Complexes. Synthesis of

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Organometallics 1995, 14, 5054-5061

5054

Enyne Metathesis Using Chromium Carbene Complexes. Synthesis of Heterocycles from Enynes Using Chromium Carbene Complexes Susumu Watanuki and Miwako Mori* Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060, Japan Received May 22, 1995@

A new synthesis of pyrrolidine and piperidine derivatives via a chromacyclobutane formed from a Fischer carbene complex and a n enyne having nitrogen in a tether was developed. As the results of the substituent effects, the reaction of enynes having the electron-donating group on the alkene with a Fischer chromium carbene complex in CH3CN afforded preferentially metathesis products, and that of the enyne having the electron-withdrawing group gave the cyclized product fused with a cyclopropane ring. The reactions of dienes, diynes, and enynes with transition metal complexes are very interesting and useful in synthetic organic chemistry. Recent studies of the reaction of enynes with Fischer carbene complexes 2,l which are easily prepared from M(CO)6 (1, M = Cr, Mo, and W) and alkyllithium followed by treatment with alkylating agent, have demonstrated a potential ring construction of bicyclic carbon skeletons (Scheme 1). It was known that the chromium carbene complex did not react with unactivated alkene.2a However, Wulff reported that treatment of enyne 3a with (methoxyethy1idene)chromium (4) in CH3CN gave cyclobutanone 5 in 45%yield. When the reaction was carried out in CH3CN-MeOH, ester 7 was obtained in good yield. He described that the chromium carbene complex did not react with unactivated alkene and cyclobutanone was produced via the [Z 21 cycloaddition of an alkene of 3a and vinylketene 6 generated by the reaction of alkyne of 3a with chromium carbene complex 4233 (Scheme 2). On the other hand, Hoye reported that the reaction of enyne 3b having an unactivated olefin with chromium carbene complex 4 afforded the cyclopropane derivative 8 in 69% yielde4 It was very interesting that the reaction of enyne 3c with 4 afforded metathesis product 9 although the yield was m ~ d e r a t e .The ~ reaction of activated olefin 3d with the Fischer carbene complex was reported by H a r ~ e yand , ~ he obtained cyclopropane derivative 8d in good yield when molybdenum carbene complex 10a was used. Katz reported that the reaction of enyne 3e with tungsten carbene complex 12 afforded

Scheme 1

M=Cr, Mo, W

Scheme 2

5

3a

MeOOC

+

Abstract published in Advance ACS Abstracts, September 15,1995. (1)Fischer, E. 0.;Maasb61, A. Angew. Chem., Int. Ed. Engl. 1984, 3,590. (2)(a) Wulff, W. D. In Advances in Metal-Organic Chemistry; Liebeskind, L. S., Ed.; JAI Press, Inc.; Greenwich, CN, 1989;Vol. 1. (b) Wulff, W. D.; Kaesler, R. W. Organometallics 1986,4,1461.(c) Kim, 0.K.; Wulff, W. D.; Jiang, W. J. Org. Chem. 1993,58,5571. (3)Hofmann, P.;Hammerle, M.; Unfried, G. New. J . Chem. 1991, 15,769. (4)(a) Hoye, T.R.; Rehberg, G. M. J. Am. Chem. SOC.1990,112, 2841. (b) Idem. Organometallics 1989,8,2070. (c) Korkowski, P.F.; Hoye, T. R.; Rydberg, D. B. R. J . Am. Chem. SOC.1988,110,2676.(d) Hoye, T.R.; Suriano, J . A. Organometallics 1992,11, 2044. ( 5 ) (a) Harvey, D. F.; Brown, M. F. J . Am. Chem. SOC.1990,112, 7806. (b) Idem. Tetrahedron Lett. 1990,31, 2529. (c) Harvey, D. F.; Lund, K. P.; Neil, D. A. Ibid. 1991,32,6311.(d) Harvey D.F.; Lund, K. P. J. Am. Chem. SOC.1991,113,5066.(e) Harvey, D.F.; Lund, K. P.; Neil, D. A. J.Am. Chem. SOC.1992,114,8424. @

0276-7333/95/2314-5054$09.00/0

6

7

metathesis product 9e in 50% yield6a,b(Schemes 3 and 4).

These products were considered to be obtained from complex I11 or W, namely, the reaction of the alkyne moiety of enyne I with the Fischer carbene complex affords vinylcarbene complex 11. If vinylcarbene complex I1 converts into vinylketene complex 111, the [2 21 cycloaddition occurs intramolecularly, and if vinylcarbene complex I1 reacts with the alkene part of the enyne intramolecularly, metallacyclobutane IV is formed. Now, we report the synthesis of heterocycles using the reaction of an enyne having nitrogen in a tether with a Fischer carbene complex. As a result, it was clear that the reaction course was controlled by the electronic factors of the substituent on the alkene' (Scheme 5).

+

Results and Discussion Reaction of an Enyne with Pentacarbonyl(eth0xyethylidene)chromium. Fischer chromium (6)(a) Katz, T.J.; Sivavec, T. M. J. Am. Chem. Soc. 1985,107,737. (b) Sivavec, T. M.; Katz, T. J . ; Chiang, M. Y.; Yang, G. Xu-Q. Organometallics 1989, 8, 1620. (c) Katz, T. J.; Yang, G. Xu-Q. Tetrahedron Lett. 1991,32,5895. (7)Preliminary work Mori, M.; Watanuki, S. J . Chem. Soc., Chem. Commun. 1992,1083.Watanuki, S.;Mori, M. Heterocycles 1993,35, 679.

0 1995 American Chemical Society

Organometallics, Vol. 14, No. 11, 1995 5055

Enyne Metathesis

Table 1. Reaction of Enyne 14a with Cr-Carbene Complex 13a

Scheme 3

____)

3b

8

Me

a

4

run

solvent

yield of 16a,%

1 2" 3 4b

CHsCN CH3CN

91 84

PhH

55 47

THF

Reaction w a s carried o u t under a CO atmosphere.

%N>O 17 (18%)

ul 3c

9

OMe

MeOOC

(°C)5M4B~

U

"bM; v

45%

..

1411, R=Ts 14b, R=Bn

Scheme 4

l5

91%

16a91% 16b 18%

~6

Scheme 7. Reaction of Enynes with 13a

0"

50%

OEt

&el

8d M=Cr (4) 34% M=MO (loa) 76%

3d

Scheme 6

COOMe

3e

ph

li'

l ) lSal 70 "C, CH3CN 4h 2) 15

?s

9.

M

e

w

e

Ts

Ts

Scheme 6

c M 55 R" =)c0(

I

OR'

(g

/

II

R"

lh

\ IV

carbene complex 13a was prepared from CrtCO)6 and MeLi followed by treatment with the Meenvein reagent (Et30+BF4-). The starting enyne 14a was prepared from N-(p-tolylsulfony1)propargylamineand allyl bromide in the presence of NaH. When a CH3CN solution of 14a and pentacarbonyl(ethoxyethy1idene)chromium (13a)was warmed a t 70 "C for 4 h and then the solution was treated with [FeCLl[FeC1~(DMF)318 (15), the cyclized product 16a fused by a three-membered ring was obtained in 91% yield. Though the reaction was carried out under carbon monoxide (1atm), the yield of 16a was not affected (Table 1,run 2). Benzene and THF can be used as solvents for this reaction, but decreased yields of 16a were shown (Table 1,runs 3 and 4). When THF was used as the solvent, the cyclopentenone derivative 17 was obtained in 18%yield along with 16a. Though the reaction mechanism for the formation of compound 17 was not clear, it was considered that reductive cyclization by a low-valent chromium complex occurs. Thus, when 14a was treated with Cr(C0)s in THF, a small amount of 17 was produced. This means that the (8)Tobinaga, S.; Kotani, E. J.Am. Chem. SOC.1972,94, 309.

168

reductive cyclization of enyne 14a occurs by a low-valent chromium complex followed by the insertion of carbon monoxide to give 17.3d,9On the other hand, when N-allylbenzylpropargylamine(14b) was treated with chromium carbene complex 13a followed by treatment with 10% HC1, cyclopropane derivative 16b was obtained in only 18%yield.1° Presumably, the nitrogen of 14b coordinates to the chromium carbene complex to give a complex mixture (Scheme 6). The above results indicate that the reaction of enynes 14a,b having an unactivated alkene with chromium carbene complex 13a affords pyrrolidine derivatives 16a,b fused by three-membered rings. Thus, the substituent effects on the alkenes of the enynes were examined. Reaction of enyne 14c with chromium carbene complex 13a afforded cyclopropane derivative 16c and cyclobutanone derivative 18c in 43% and 46% yields, respectively. However, the reaction of enyne 14e having an activated alkene with 13a gave cyclopropane derivative 16e in 71%yield as the sole product (Scheme 7). Subsequently, the reaction of enyne E-14d having a phenyl group on the alkene with 13a was examined. (9)Jordi, L.; Segundo, A,; Camps, F.; Ricart, S.; Moreto, J. M. Organometallics 1993,12, 3795. (10)Hoye, T.R.; Suriano, J. A. J.Am. Chem SOC.l99S,115, 1154. (11)Katz has reported that the reaction of the metal carbene complex with the enyne having nitrogen in a tether afforded the cyclopropane derivative. The carbene complex was made to absorb silica gel, and the reaction was carried out with no solvent.5c

5056 Organometallics, Vol. 14, No. 11, 1995

Watanuki and Mori

Scheme 8. Reaction of E- and Z14d with 13a Ph

4 N ''

111

1) 138, CH&N 70°C,4 h

-

2) 15

Ts

Scheme 9. Reaction of E-14d with 13c

N ''

5 14d

2) [FeCI,(DMF)d[FeCI.,i

TS

E-1 4d

Hw+H 19 53%

16d 7%

18d 9%

N

N

TS

Ts

16d 17%

16d' 8%

Table 2. Reaction of Enyne 14 with Cr-Carbene Complexes yield, % X ._

2-14d

19 49%

19' 7%

substrate

NO2

19

16

18

4

75

1:19

46

18 7 6

8

3:l

9

7.7:l

14f 14g

H

E-14d

53

Me

14h

62

c1

l9:16

l:o

Scheme 10. Reaction of Enyne Having a p-Substituted Phenyl Group on the Alkene X

Surprisingly, the metathesis product 19 was obtained in 53% yield as a main product along with cyclopropane derivative 16d (7%yield) and cyclobutanone derivative 18d (9% yield).12 The NOE experiments of the ring junction proton Ha with the aromatic proton of compound 16d or of the ring junction proton Hb with the aromatic proton of compound 18d suggested that the reaction proceeded stereoselectively. On the other hand, the reaction of 2-14d with 13a was carried out in a similar manner to give only metathesis products, 19 and 19, in 56% yield (19/19 = 7/11. Neither the cyclopropane derivative nor the cyclobutanone derivative was obtained in this case because of the steric repulsion between the phenyl group and the five-membered ring of 20 on the transition state for the formation of the three- or four-membered ring. When a CH3CN solution of E-14d with tungsten carbene complex 13c was refluxed for 7 days, cyclopropane derivative 16d was obtained in only 19% yield along with 16d in 17%yield. In this case, the reaction did not proceed with a stereoselective manner (Schemes 8 and 9). Substituent Effects of the Aromatic Ring on the Alkene for the Reaction of an Enyne with a Chromium Carbene Complex. It was very interesting that the enyne having an unsubstituted alkene afforded the cyclized product 1%fused by a threemembered ring and the metathesis products 19 were obtained from the enynes having a phenyl or methyl group3 on the alkene.13 If the formation of the metathesis product 19 or of the cyclopropane derivative 16 was controlled by the electronic factor of the substituent on the alkene, the substituent effect on the aromatic ring should be observed. The reactions of enynes 14f-h with ~

~~~

(12) Though the reaction was carried out under carbon monoxide, the yield of 18d was not increased and compounds 19, 16d, and 1Sd were obtained in 26%, 5%, and 6% yield, respectively. (13) A metathesis reaction using a chromium carbene complex and a n electron-donating olefin is reported by Fischer: Fischer, E. 0. J. Organometal. Chem. 1973, 56, 279.

1) 138, CH3CN 70 "C, 4 h

'1'

2)15

LN) Ts 14f, 14g, 14h

*

Y

M

Ts 19

Ts 16fs16gv 16h

Ts 18f, 18g, 18h

chromium carbene complex 13a were carried out in CH3CN upon heating, and the results were shown in Table 2. The reaction of compound 14g having an electronwithdrawing group on the aromatic ring with 13a increased the ratio of the cyclopropane derivative 16 to the metathesis product 19 (3:l).It was very interesting that compound 14f having ap-nitrophenyl group on the alkene afforded the cyclopropane derivative 16f as a main product. In the case of the reaction of 14h, the metathesis product 19 was obtained as the main product and the cyclopropane derivative 16 was not produced. This means that the metathesis reaction is accelerated by the electron-donating group on the aromatic ring (Scheme 10). Possible Reaction Course for the Reaction of Enynes with Chromium Carbene Complexes. The mechanism for the reaction of enyne 14 with chromium carbene complex 13a is not clear yet. However, the reaction course could be considered on the basis of the distribution of the products. The reaction of the alkyne part of enyne 14 with chromium carbene complex 13a gave vinylcarbene complex 21, which would form chromium ketene complex 22 or chromacyclobutane 24. From the former pathway, the [2 + 21 cycloaddition of ketene and olefin would proceed, which affords cyclobutanone derivative 18 via 23. On the other hand,

Organometallics, Vol. 14,No.11, 1995 5057

Enyne Metathesis

Scheme 11. Reaction Mechanism R

-p y R

2)'

Metathesis c -

\=CrLn

+

Ts

Ts

14

21

\

26

\

25

\

Reductive elimination

19

'hoEt 16

Ts

Ts

23

22

Ts 27

cyclopropane derivative 27 and metathesis product 26 were obtained from chromacyclobutane 24. If bond cleavage of chromacyclobutane occurs, alkylidenecarbene 26 is formed along with metathesis product 26. If the reductive elimination occurs from 24, cyclopropane derivative 27 is formed. The unsubstituted alkene 14a (R = H) and the alkene 14f having a p-nitrophenyl group on the alkene afforded the cyclopropane derivatives 16a,f. In these cases, compounds 14a,f afforded only the chromacyclobutanes 24a,f. They afforded the cyclopropanes 16a,f in good yields because corresponding (alkylidenekhromium carbene complexes 26a,f were unstable. On the other hand, the electron-donating group on the alkene accelerated the metathesis reaction13because the alkylidene carbene complex 26 generated from chromacyclobutane24 was stabilized by these groups. Thus enyne 14h afforded only metathesis product 19. Since the [2 21 cycloaddition reaction was controlled by a HOMOLUMO interaction, it should be accelerated by the alkene having an electron-donating group. In the reaction of 14c with 13a, cyclobutanone derivative 18c was obtained in 46% yield along with cyclopropane derivative 16c (43% yield). However, cyclopropane derivative 16a was a main product when compound 14a was treated with chromium carbene complex 13a. Since the higher HOMO energy of 14c compared with that of 14a favors the [2 21 cycloaddition of ketene and alkene, the formation of cyclobutanone derivative would be accelerated. It could be understood when compound 14e was treated with 13a, only cyclopropane derivative 16e was obtained (Scheme

+

+

11).

Reaction of Enynes with Pentacarbonyl(eth0xybenzy1idene)chromium. Subsequently, the reaction of enyne with pentacarbonyl(ethoxybenzy1idene)-chromium (28),which was prepared from Cr(C0)s and PhLi followed by treatment with Et30+BF4-, was examined. A CH3CN solution of 14a with chromium carbene complex 28 was warmed at 70 "C for 4 h followed by treatment with 10%HC1 to give cyclopropane derivative 29a in 79%yield. When E-14d was treated with 28 in CHsCN, metathesis product 30 was obtained in 69% yield. The reaction of 14c with 28 afforded cyclopropane derivative 29c, cyclobutanone derivative 31c, and indanone derivative 3214 in 32%, 25%, and 12% yields, respectively (Scheme 12). ~

~~

~~~

(14)(a) Wulff, W. D.; Tang, P. C.; McCallum, K. S.; Yang, D. C.; Gilbertson, S. R. Tetrahedron 1986, 41, 5813. (b) Yamashita, A. Tetrahedron Lett. 1986,27, 5915.

Scheme 12. Reaction of Enynes with 28 OEt

111I

h' Ts

Ts 79%

Ph I

N

2) 10% HCI

Ts 14a

29a

mPh

1) 28, CHaCN 70°C,4h

N Ts

2) 10% HCI

69%

30

E-14d

'$/

'1'

N

1) 28, CH3CN 70°C,4 h 2) 10% HCI

M

14c

e

h

o + Ts 2%

N

P

o

.-

T.2

32%

3 1 ~25%

h

yN@ /

+ TS .-

32 12%

Synthesis of Piperidine Derivatives Using Chromium Carbene Complexes. Next, we attempted the synthesis of piperidine derivatives using the reaction of enynes with chromium carbene complexes. Recently, Harvey reported the synthesis of pyran derivative 34 from allyl ether 33 using molybdenum carbene complex However, homoallyl ether 35 did not afford the cyclized product. They claimed that the reason is due t o the acidity at the carbon a t o the molybdenum carbene carbon of 36 (Scheme 13). When propargylamine derivative 39a was treated with chromium carbene complex 13a in CH3CN a t 70 "C for 4 h, piperidine derivative 40a fused by a threemembered ring was obtained in 46% yield. In this reaction, the use of CH3CN was found to be superior to THF and benzene (Table 3). In a similar manner, the reaction of enynes 39b,c with 13a afforded piperidine derivatives 40b,c fused by three-membered rings in good yields, respectively. On the other hand, compound 39d having a phenyl group on the alkene also afforded metathesis product 40d, though the yield was low. The substituent effects for the synthesis of piperidine de-

5058 Organometallics, Vol. 14,No. 11, 1995

Scheme 13. Formation of the Pyran Ring

33

37% 34

' -0

-

OMe MoLn 36

OMe MoLn 37 H

Table 3. Reaction of Enyne 39a with Cr-Carbene Complex 13a run conditions yield of ma, % 1 CHsCN, 70 "C, 4 h 46 36 2 THF, reflux, 4 h 3 PhH, 70 "C, 4 h 39 Scheme 14. Synthesis of the Piperidine Ring U

4Qa

39a

/

/"'

\\

(N) Ts 39b

1) 13a

2) 15

21

Ts 4Qb

40%

MeOOC

N 39c Ts

1) 13a

~

6

2) 15 55% Ts 4Qc

Ph

Ts 39d

Ts 15%

4Qd

rivatives were the same as those for the synthesis of pyrrolidine derivatives (Scheme 14). In conclusion, reactions of enynes with Fischer chromium carbene complexes gave the various pyrrolidine and piperidine derivatives. The reaction products were dramatically affected by the substituents on the alkene. The reaction of a compound having an electron-donating group on the alkene with a chromium carbene complex gave a metathesis product, and the electron-withdrawing group promotes the formation of a three-membered ring. Experimental Section All manipulations were performed under an argon atmosphere using standard Schlenk techniques, and all the reaction

Watanuki and Mori solutions were degassed through freeze-pump-thaw cycles. Solvents were distilled under an argon atmosphere from sodium benzophenone ketyl (THF) or CaH2 (CH2C12). All other reagents and solvents were purified when necessary using standard procedures. Column chromatography was performed on silica gel 60 (70-230 mesh, 60 A), and flash chromatography was performed on silica gel 60 (230-400 mesh, 60 A) using the indicated solvent. Melting points are uncorrected. Preparations of enynes 14a-c were already reported.'* General Procedure for the Reaction of Fischer Carbene Complexes with Enynes. An appropriate solution of Fischer carbene complex (1.2 equiv) and enyne (1equiv) was degassed through a freeze-pump-thaw cycle, and the solution was stirred at an apropriate temperature. After cooling, a CH3CN solution of [FeC12(DMF)3l[FeCl41(3.6 equiv) or 10% HCl was added and the solution was stirred overnight. Water was added, and the organic layer was extracted with ethyl acetate. The organic layer was washed with brine, dried over Na2S04, and concentrated. The residue was purified by silica gel column chromatography. Reaction of Enyne 14a with 13a. The crude product, which was prepared from 14a (50.0 mg, 0.20 mmol) and 13a (64 mg, 0.241 mmol) in CH3CN (1.5 mL) at 70 "C for 4 h followed by treatment with [FeC12(DMF)31[FeC14](393 mg, 0.723 mmol), was purified by silica gel chromatography (ethyl acetate-hexane, 1:2) to give 16a. reL(1S,5S)-1-(2-Oxopropyl)-3-0,-tolylsulfonyl)-3-azabicyclo[3.1.0]hexane (16a):53.5 mg, 91%; IR (Nujol) v 1715, 1597, 1341, 1161 em-'; 'H-NMR (CDC13) 6 0.56 (dd, J = 5.9, 7.8 Hz,l H), 0.70 (dd, J = 4.4,5.9 Hz, 1H), 1.26 (ddd, J = 3.9, 4.4, 7.8 Hz, 1H), 2.09 (s, 3 H), 2.44 (5, 3 H), 2.46 (d, J = 17.1 Hz, 1H), 2.59 (d, J = 17.1 Hz, 1 HI, 2.89 (d, J = 9.3 Hz, 1 HI, 3.15 (dd, J = 3.9, 9.3 Hz, 1 H), 3.51 (d, J = 9.3 Hz, 1H), 3.62 ( d , J = 9 . 3 H z , l H ) , 7 . 3 2 ( d , J = 8.3 H z , 2 H),7.67 ( d , J = 8.3 Hz, 2 H); W N M R (CDC13)6 206.5, 143.4, 133.7, 129.6, 127.5, 52.8, 49.7 47.0, 30.0, 25.6, 21.5, 21.3, 13.7; MS m l z 293 (M+), 277,250,187,155,138,gl (base peak); HRMS ( m l z )calcd for C I ~ H I ~ N O293.1073, ~S found 293.1079. Anal. Calcd for C~~H~SNO C,~61.41; S : H, 6.53; N, 4.77; S, 10.93. Found: C, 61.36; H, 6.54; N, 4.74; S, 10.92. 7-Oxo-3-~-tolylsulfonyl)-3-azabicyclo[3.3.0] oct-5-ene (17): mp 139 "C; IR (Nujol) v 1713, 1651, 1599, 1161 cm-'; 'H-NMR (CDC13) 6 2.06 (dd, J = 3.5, 18.1 Hz, 1 H), 2.44 (s, 3 H), 2.59 (dd, J = 6.3, 18.1 Hz, 1HI, 2.62 (dd, J = 9.3, 11.2 Hz, 1 HI, 3.10-3.20 (m, 1 HI, 4.01 (d, J = 9.3 Hz, 1 HI, 4.03 (d, J = 16.6 Hz, 1 H), 4.34 (d, J = 16.6 Hz, 1 H), 5.99 (brs, 1 H), 7.35 (d, J = 8.3 Hz, 2 H), 7.73 (d, J = 8.3 Hz, 2 H); MS m l z 277 (M+), 155, 122, 94, 91 (base peak); HRMS ( m l z )calcd for CMH~~NO 277.0773, ~S found 277.0784. Anal. Calcd for CMHISNO~S: C, 60.63; H, 5.45; N, 5.05; S, 11.56. Found: C, 60.45; H, 5.47, N, 4.87; S, 11.71. Reaction of Enyne 14b with 13a. The crude product, which was prepared from 14b (45.8 mg, 0.247 mmol) and 13a (77.7 mg, 0.294 mmol) in CHsCN (2.5 mL) at 70 "C for 4 h followed by treatment with 10% HCl and then K2CO3, was purified by silica gel chromatography (ethyl acetate-hexane, 1:4-1:O) to give 14b. reZ-~1S,SS)-3-Benzyl-l-(2-oxopropyl~-~-~abicyclo[3.l.Olhexane (14b):10.4 mg, 18%;IR (neat) v 1711 em-'; 'H-NMR (CDC13) 6 0.46 (dd, J = 3.2, 7.2 Hz,l H), 1.19-1.28 (m, 2 H), 2.20 (5, 3 H), 2.26 (d, J = 8.5 Hz, 1 HI, 2.47 (d, J = 15.8 Hz, 1 H), 2.48 (dd, J = 2.9, 8.6 Hz, 1 HI, 2.70 (d, J = 15.8 Hz, 1 H), 2.98 (d, J = 8.6 Hz, lH), 3.04 (d, J = 8.5 Hz, lH), 3.64 (s, 2 HI, 7.21-7.36 (m, 5 HI; MS m l z 229 (M+),186, 172, 152, 138, 91, 43 (base peak); HRMS ( m l z ) calcd for C15H19N0 229.1467, found 229.1480. Reaction of Enyne 14c with 13a. The crude product, which was prepared from 14c (52.4 mg, 0.20 mmol) and 13a (62.9mg, 0.238 mmol) in CH3CN (2.0 mL) at 70 "C for 4 h followed by treatment with [FeC12(DMF)31[FeC14](390 mg, 0.717 mmol), was purified by silica gel chromatography (ethyl

Enyne Metathesis

Organometallics, Vol. 14,No. 11, 1995 5059

3-2-(Oxopropenyl)-1-(p-t~lylsulfonyl)-3,3-didehydropyrrolidine (19'): IR (neat) v 1693,1629,1598,1346,1163cm-'; reL(1S,5S)-5-Methyl-l-(2-oxopropyl)-3-(p-tolylsulfonyl)- 'H-NMR (CDC13)6 2.15-1.95 (m, 2 H), 2.17 (s, 3 H), 2,43 (s, 3 H), 4.40-3.10 (m, 4 H), 6.17 (brs, 1 H), 7.32 (d, J = 8.3 Hz, 3-azabicyclo[3.l.0]hexane (14c):mp 104-5 "C; IR (Nyiol) 2 H), 7.83 (d, J = 8.3 Hz, 2 H); MS m l z 279 (M+),236,155,91 v 1716, 1344, 1157 cm-l; 'H-NMR (CDC13) 6 0.28 (d, J = 5.2 (base peak), 82.; HRMS ( m l z )calcd for C14H17N03S 279.0929, Hz, 1H), 0.87 (d, J = 5.2 Hz, 1HI, 1.05 (s, 3 H), 2.12 (9, 3 H), found 279.0948. 2.44(s,3H),2.89(d, J = 9 . 1 H z , 2 H ) , 2 . 9 0 ( d , J = 9 . 1 H z , 2 Reaction ofE-14dwith 13c. The reaction procedure was H),3.54(d, J = 9 . 0 H z , l H ) , 3 . 6 0 ( d , J = g . O H z , l H ) , 7 . 3 2 ( d , same as that of the reaction of enyne with 13a. A crude J = 8.1 Hz, 2 H), 7.67 (d, J = 8.1 Hz, 2 H); MS m l z 307 (M+), 264,152 (base peak), 108,91,43. Anal. Calcd for C I ~ H Z ~ N O ~ S :product, which was prepared from 2-14d (50.0 mg, 0.154 mmol) and 13c (73.0 mg, 0.184 mmol) in CH3CN (1.5 mL) C, 62.51; H, 6.89; N, 4.56; S, 10.43. Found: C, 62.58; H, 6.85; under refluxing for 67 h followed by treatment with [FeClzN, 4.58; S, 10.49. (DMF)3][FeCld](301 mg, 554 mmol), was purified by silica gel reL(1R,5S)-5-Methyl-7-oxo-l-(2-oxopropyl)-3-(p-tolylchromatography (ethyl acetate-hexane, 1:3) to give 16d (9.7 sulfonyl)-3-azabicyclo[3.2.O]heptane(18~): mp 143 "C; IR mg, 17%) and 16d (4.6 mg, 8%). (Nujol) v 1776, 1715, 1342, 1160 cm-'; 'H-NMR (CDCl3) 6 1.18 reZ-(lR,5R,W)-1-(2-Oxopropyl)-6-phenyl-3-0,-tolylsul(8, 3 H), 2.10 (9, 3 H), 2.45 (9, 3 H), 2.63 (d, J = 9.8 Hz, 1 H), fonyl)-3-azabicyclo[3.1.0]hexane(16d): IR (KBr) v 1715, 2.66 (d, J = 18.9 Hz, 1 H), 2.70 (d, J = 9.8 Hz, 1 H), 2.71 (d, 1597, 1340, 1160 cm-'; 'H-NMR (CDC13) 6 1.71 (dd, J = 4.8, J = 18.9 Hz, 1H), 3.08 (d, J = 18.1Hz, 1H), 3.15 (d, J = 18.1 8.46 Hz, 1H), 2.08 (d, J = 8.4 Hz, 1H), 2.17 (s, 3 H), 2.38 (s, Hz, 1 H), 3.64 (d, J = 9.8 Hz, 1H), 3.77 (d, J =9.8 Hz, 1 H), 3 H), 2.54 (d, J = 18.0 Hz, 1 H), 3.02 (d, J = 18.0 Hz, 1 H), 7.34 (d, J = 8.3 Hz, 2 H), 7.68 (d, J = 8.3 Hz, 2 H); MS m l z 3.15 (d, J = 9.5 Hz, 1 H), 3.40 (d, J = 9.5 Hz, 1HI, 3.52 (dd, 335 (M+), 293, 250, 180, 155, 138, 91, 43 (base peak). Anal. J =4.8,9.5 Hz, 1 H), 3.56 ( d , J = 9.5 Hz, 1H), 7.72-7.38 (m, Calcd for C17H21N04S: C, 60.88; H, 6.31; N, 4.18; S, 9.56. 7 H), 7.76 (d, J = 8.4 Hz, 2 H); MS m l z 369 (M+),326, 278, Found: C, 60.82; H, 6.29; N, 4.14; S, 9.58. 214, 155, 117, 91 (base peak); HRMS ( m l z )calcd for C21H23Reaction of E-14dwith 13a. The crude product, which NO3S 369.1399, found 369.1386. was prepared from E-14d(50.0 mg, 0.154 mmol) and 13a (49.0 Reaction of 14e with 13a. The crude product, which was mg, 0.184 mmol) in CH3CN (1.5 mL) at 70 "C for 4 h followed prepared from 14e (56.5 mg, 0.184 mmol) and 13a (58.7 mg, by treatment with [FeCl2(DMF)31[FeC141(300mg, 0.552 mmol), 0.222 mmol) in CH3CN (1.8 mL) at 70 "C for 4 h followed by acetate-hexane, 15-1:l) to give 14c (26.1 mg, 43%) and 18c (30.9 mg, 46%).

was purified by silica gel chromatography (ethyl acetatetreatment with [FeC12(DMF)31[FeCLI(360 mg, 662 mmol), was hexane, 1:5-1:l) to give 19 (22.8 mg, 53%), 16d (4.1 mg, 7%), purified by silica gel chromatography (ethyl acetate-hexane, and 18d (5.5 mg, 9%). 1:2-1:3) t o give 17e (46 mg, 71%). ~3-(2-Oxopropyl)-l-(p-tolylsulfonyl)-2,5-dihydro- reZ-(lR,5R,6R)-6-(Methoxycarbonyl)-l-(2-oxopropyl)pyrrole (19):IR (neat) v 1717, 1630, 1597, 1341, 1161 cm-l; 3-@-tolylsulfonyl)-3-azabicyclo[3.l.0lhexane (16e): mp 'H-NMR (CDC13) 6 2.21 (9, 3 H), 2.43 (9, 3 HI, 3.18 (s, 2 H), 138 "C; IR (Nujol) v 1726, 1719, 1348, 1161 cm-l; lH-NMR 4.09 (brs, 4 H), 5.48 (brs, 1H), 7.32 (d, J = 8.3 Hz, 2 H), 7.72 (CDC13) 6 1.88 (dd, J =3.4, 3.9 Hz, 1H), 1.93 (d, J =3.9 Hz, (d, J = 8.3 Hz, 2 H); 13C-NMR(CDC13) 6 204.4 142.5, 134.1, 1 H), 2.06 (s, 3 H), 2.44 (s, 3 H), 2.78 (d, J = 18.4 Hz, 1 H), 132.2, 129.8, 127.4, 122.8,56.4, 54.8,43.3,29.7,21.5;MSmlz 2.94 (d, J =10.1 Hz, 1 H), 3.05 (d, J = 18.4 Hz, 1H), 3.23 (dd, 279 (M+),236, 155, 91 (base peak), 82; HRMS ( m l z )calcd for J = 3.4, 9.6 Hz, 1H), 3.62 (d, J = 10.1 Hz, 1H), 3.65 (s, 3 H), C14H17N03S 279.0929, found 279.0916. Anal. Calcd for 3.73 (d, J = 9.6 Hz, 1H), 7.34 (d, J = 8.1 Hz, 2 H), 7.67 (d, J C14H17N03S: C, 60.19; H, 6.13; N, 5.01; S, 11.48. Found: C, = 8.1 Hz, 2 H); MS m l z 351 (M+),320, 308, 196 (base peak), 60.33; H, 6.30; N, 4.93; S, 11.44. 155, 136, 91. Anal. Calcd for C ~ ~ H ~ I N O C,~58.10; S : H, 6.02; rel-(1R,5R,6R)-1-(2-0xopropyl)-6-phenyl-3-(p-tolylsul-N, 3.99; S, 9.12. Found: C, 58.03; H, 6.03; N, 3.96; S, 9.14. fonyl)-3-azabicyclo[3.1.O]hexane(16d): IR (Nujol) v 1715, Reaction of 14f with 13a. The crude product, which was 1599, 1345, 1163 cm-l; 'H-NMR (CDC13) 6 1.76 (s, 3 H), 1.83 prepared from 14f (50 mg, 0.135 mmol) and 13a (43.0 mg, (dd, J = 3.9, 4.4 Hz, 1H), 2.20 (d, J =4.4 Hz, 1H), 2.30 (d, J 0.162 mmol) in CH3CN (1.4 mL) at 70 "C for 4 h followed by = 18.1 Hz, 1H), 2.36 (d, J = 18.1Hz, 1H), 2.44 ( 8 , 3 H), 3.04 treatment with [FeC12(DMF)3][FeC141(264 mg, 0.486 mmol), (d, J = 9.3 Hz, 1 H), 3.34 (dd, J = 4.4, 9.3 Hz. 1 H), 3.70 (d, was purified by silica gel chromatography (ethyl acetateJ = 9.3 Hz, 1 H), 3.91 (d, J = 9.3 Hz, 1 H), 7.00-7.04 (m, 2 hexane, 1:2-1:l) to give 19 (1.5 mg, 4%) and 16f (42.2 mg, H), 7.22-7.28 (m, 3 H), 7.32-7.36 (m, 2 H), 7.70-7.75 (m, 2 75%). H); 13C-NMR(CDC13)6 206.6, 143.5,136.7,133.8,129.7,128.6, rel-(1R,5R,6R)-6-(4-Nitrophenyl)-l-(2-oxopropyl)[email protected], 127.5,126.5,54.1, 50.1,42.1,31.1,30.0,28.9,25.6,21.6; tolylsulfonyl)-3-azabicyclo[3.1.0lhexane(160:mp 153 "C; MS m l z 369 (M+),326, 278, 214, 156, 117 (base peak), 91; IR (Nujol) v 1715, 1597, 1516, 1343, 1161 cm-l; 'H-NMR HRMS ( m l z )calcd for C21H23N03S 369.1399, found 369.1373. (CDCl3) 6 1.83(s, 3 H), 1.92 (dd, J = 3.9,4.4 Hz, 1H), 2.30 (d, mZ-( ~R,SR,~S)-~-OX~ 1-(2-oxopropyl)-6-phenyl-3-(p-tolyl- J = 18.6 Hz, 1H), 2.36 (d, J = 4.4 Hz, 1H), 2.42 (d, J = 18.6 Hz, 1 H),2.45 (s, 3 H ) , 2 , 9 8 ( d , J = 9.8 Hz, 1H),3.33( d d , J = sulfonyl)%-azabicyclo[3.2.0]heptane (18d):IR (Nujol) Y 3.9, 9.3 Hz, 1H), 3 . 7 4 ( d , J = 9.3 Hz,lH),3.96 ( d , J = 9.8 Hz, 1790, 1715, 1597, 1362, 1169 cm-l; 'H-NMR (CDC13) 6 1.78 1H), 7.20 (d, J = 8.8 Hz, 2 H), 7.36 (d, J = 8.3 Hz, 2 H), 7.72 (9, 3 H), 2.24 (d, J = 18.6 Hz, 1H), 2.39 (d, J = 18.6 Hz, 1H), (d, J = 8.3 Hz, 2 H), 8.12 (d, J = 8.8 Hz, 2 H); MS m l z 414 2.48 (s, 3 H), 3.27 (brs, 1 H), 3.31 (ddd, J = 2.0, 3.4, 3.4 Hz, 1 (M+),371,259,116,91,43 (base peak); HRMS ( m l z )calcd for H), 3.79 (d, J = 10.7 Hz, 1H), 3.99 (dd, J =3.4, 10.7 Hz, 1H), 4.06 (dd, J = 3.4, 10.7 Hz, 1 H), 4.48 (d, J = 10.7 Hz, 1 H), C ~ ~ H Z ~ N414.1249, ~ O ~ S found 414.1259. Anal. Calcd for 6.95-6.99 (m, 2 H), 7.21-7.28 (m, 3 H), 7.40 (d, J = 7.8 Hz, 2 C~IHZZNZO&~: C, 60.86; H, 5.35; N, 6.76; S, 7.74. Found: C, 60.60, H, 5.30; N, 6.58; S, 7.63. H), 7.78 (d, J = 7.8 Hz, 2 H); 1%-NMR (CDCl3) 6 207.3,204.8, 144.1, 137.1, 134.0, 130.0, 128.8, 127.5, 66.7, 58.3, 57.4, 53.3, Reaction of 14g with 13a. The crude product, which was 43.6, 40.3, 30.4, 21.6; MS m l z 397 (M+), 354, 242, 155, 117 prepared from 14g (50 mg, 0.139 mmol) and 13a (44.0 mg, (base peak), 91; HRMS ( m l z )calcd for CzzHz3N04S 397.1347, 0.167 mmol) in CH3CN (1.4 mL) at 70 "C for 4 h followed by found 397.1331. treatment with [FeC12(DMF)3][FeC141(272 mg, 0.500 mmol), was purified by silica gel chromatography (ethyl acetateReaction of Z-14dwith 13a. The crude product, which hexane, k3-1:2) to give 19 (17.8 mg, 46%), 16gU0.2mg, 18%) was prepared from Z-14d(100 mg, 0.308 mmol) and 13a (98.0 and 18g (5.0 mg, 8%). mg, 0.368 mmol) in CH3CN (3.0 mL) at 70 "C for 4 h followed rei-(1R,5R,6R)-6-(4-Chlorophenyl)-l-(2-oxopropyl)-3by treatment with [FeCl2(DMF)31[FeC141(600mg, 1.10 mmol), (p-tolylsulfonyl)-3-azabicyclo[3.1.O]hexane (leg): IR (Nuwas purified by silica gel chromatography (ethyl acetatejol) v 1713, 1597, 1343, 1161 cm-'; 'H-NMR (CDCl3) 6 1.77 hexane, 1:4-1:2) to give 19 (42.2 mg, 49%) and 1 9 (6 mg, 7%).

5060 Organometallics, Vol. 14, NO. 11, 1995 (dd, J = 3.9, 4.4 Hz, 1H), 1.81 (s, 3 H), 2.20 (d, J = 4.4 Hz, 1 H),2.29 ( d , J = 18.6 Hz, 1H),2.35 ( d , J = 18.6 Hz, 1H),2.44 (s, 3 H), 2.98 (d, J = 9.3 Hz, 1 H), 3.31 (dd, J = 3.9, 9.3 Hz, 1 H), 3.69 (d, J = 9.3 Hz, 1H), 3.91 (d, J = 9.3 Hz, 1H), 6.69 (d, J=8.3Hz,2H),7.22(d,J= 8.3Hz,2H),7.34(d,J=8.3Hz, 2 H), 7.71 (d, J = 8.3 Hz, 2 H); MS m l z 403 (M+),306, 248, 155, 151, 91, 43 (base peak); HRMS ( m l z )calcd for C21H22N03SC1403.1009, found 403.1013. rel-(lR,5R,6S)-6-(4Chlorophenyl)-7-oxo-l-(2-oxopropyl)3-(p-tolylsulfonyl)-3-azabicyclo[3.2.0lheptane(18g): IR (Nujol) v 1786,1717,1597,1354,1165cm-'; 'H-NMR (CDC13)

Watanuki and Mori rel-(lR,5S)-5-Methyl-7-oxo-1-(2-oxo-2-phenylethyl)-3@-tolylsulufonyl)-3-azabicyclo[3.2.0]heptane (30c): mp 165-6 "C; IR (Nujol) Y 1773,1684,1376,1160 cm-l; 'H-NMR (CDC13)6 1.22 (9, 3 H), 2.47 (s, 3 H), 2.75 (d, J =9.3 Hz, 1HI, 2.81 (d, J = 9.3 Hz, 1 H), 3.15 (d, J = 18.0 Hz, 1 H), 3.24 (d,

J=18.9Hz,1H),3.30(d,J=18.0Hz,1H),3.32(d,J=18.9 Hz, 1 H), 3.69 (d, J = 9.8 Hz, 1 H), 3.85 (d, J = 9.8 Hz, 1 H), 7.36 (d, J = 8.2 Hz, 2 H), 7.40-7.48 (m, 2 HI, 7.54-7.61 (m, 1 H), 7.71 (d, J = 8.2 Hz, 2 H), 7.84 (d, J = 8.3 Hz, 2 H); MS m l z 397 (M+), 354, 250, 242, 200, 155, 105 (base peak), 91. Anal. Calcd for CzzH23N04S: C, 66.48; H, 5.83; N, 3.52; S, 61.84(s,3H),2.22(d,J=19.0Hz,1H),2.45(d,J=19.0Hz,8.07. Found: C, 66.51; H, 5.77; N, 3.75; S, 7.79. 3-[2-Aza-4-methyl-2-(p-tolylsulfonyl)-4-pentenyll1 H), 2.48 (s, 3 H), 3.28 (brs, 2 H), 3.76 (d, J = 10.7 Hz, 1 H), indanone (31): IR (neat) Y 1717,1654,1599,1339,1160cm-'; 3.98 (dd, J = 2.9, 10.7 Hz, 1 H), 4.05 (dd, J = 2.9, 10.7 Hz, 1 IH-NMR (CDC13) 6 1.72 (s,3 H), 2.43 (s,3 H), 3.22 (dd, J = H), 4.43 (d, J = 10.7 Hz, 1 H), 6.92 (d, J = 8.3 Hz, 2 H), 7.22 3.3, 19.4 Hz, 1H), 2.79 (dd, J =7.4, 19.4 Hz, 1H), 3.22 (dd, J (d, J =8.3 Hz, 2 H ) , 7.40(d, J = 8 . 3 Hz, 2 H ) , 7.76(d, J = 8 . 3 = 11.2, 14.1 Hz, 1H), 3.38 (dd, J =4.9, 14.1 Hz, 1H), 3.68 (d, Hz, 2 H); MS m l z 433, 431 (M+),388, 276, 151, 91,43 (base J = 14.9 Hz, 1H), 3.72-3.82 (m, 1H), 3.82 (d, J = 14.9 Hz, 1 peak); HRMS ( m l z )calcd for C2zH2zN04SC1433.0929, found H), 4.90 (s, 3 H), 4.93 (s,1 H), 7.32 (d, J = 8.2 Hz, 2 H), 7.37433.0944. 7.44 (m, 1 H), 7.50 (d, J = 7.2 Hz, 2 H), 7.56-7.62 (m, 1 H), Reaction of 14h with 13a. The crude product, which was 7.70 (d, J = 8.2 Hz, 2 H), 7.75 (d, J = 7.5 Hz, 1 H); MS m l z prepared from 14h (50 mg, 0.147 mmol) and 13a (47.0 mg, 369 (M+),366,238 (base peak), 155,136,91,55; HRMS ( m l z ) 0.177 mmol) in CH3CN (1.5 mL) at 70 "C for 4 h followed by

calcd for ClzHlflOzS 238.0902, found 238.0904. Reaction of E-14dwith 28. The crude product, which was prepared from E-14d (200.8 mg, 0.617 mmol) and 28 (242.4 mg, 0.743 mmol) in CH3CN (6.2 mL) at 70 "C for 4 h followed by treatment with 10% HCl, was purified by silica gel chromatography (ethyl acetate-hexane, 1:5-1:3) to give 30d (145 mg, 69%). 3-(2-Oxo-2-phenylethyl)l-(p-tolylsulfonyl)-2,5-dihydropyrrole (30d): IR (neat) v 1687, 1600, 1340, 1160 cm-l; J=1.0,3.4,3.4Hz,1H),3.71(d,J=10.7Hz,1H),3.90(dd,'H-NMR (CDC13)6 2.41 (s, 3 H), 3.70 (s, 2 H), 4.13 (brs, 4 H), 6.48 (brs, 1 H), 7.30 (d, J = 8.3 Hz, 2 H), 7.32-7.64 (m, 3 H), J = 3.4, 10.7 Hz, 1 H), 3.98 (dd, J = 3.4, 10.7 Hz, 1 H), 4.38 7.71 (d, J = 8.3 Hz, 2 H), 7.88 (dd, J = 2.0, 7.9 Hz, 2 HI; MS (d, J = 10.7 Hz, 1 H), 6.78 (d, J = 8.3 Hz, 2 HI, 6.98 (d, J = m l z 341 (M+),236,186,155,105 (base peak), 91. Anal. Calcd 7.8 Hz, 2 H), 7.33 (d, J = 7.8 Hz, 2 H), 7.70 (d, J = 8.3 Hz, 2 for C19H19N03S: C, 66.84; H, 5.61; N, 4.10; S, 9.39. Found: H); MS m l z 411 (M+),368,256,131 (base peak), 91,43; HRMS C, 66.75; H, 5.76; N, 3.99; S, 9.03. ( m l z )calcd for C Z ~ H ~ ~ N 411.1504, O ~ S found 411.1485. Reaction of 39a with 13a. The crude product, which was Reaction of 14a with 28. The crude product, which was prepared from 41a (30 mg, 0.114 mmol) and 13a (36 mg, 0.137 prepared from 14a (149.6 mg, 0.6 mmol) and 28 (235.7 mg, mmol) in CH3CN (1.1 mL) at 70 "C for 4 h followed by 0.722 mmol) in CH3CN (6.0 mL) at 70 "C for 4 h followed by treatment with [FeCl~(DMF)3I[FeC41(223 mg, 0.41 mmol), was treatment with 10% HC1, was purified by silica gel chromapurified by silica gel chromatography (ethyl acetate-hexane, tography (ethyl acetate-hexane, 1:5-1:3) to give 29a (168.6 1:3-1:2) t o give 40a (16.1 mg, 46%). mg, 79%) as a colorless oil. rel-(1S,6R)-l-(2-Oxopropyl)-3-(p-tolylsulfonyl)-3-azarei-(is,5s)-l-(2-Oxo-2-phenylethyl)-3-(p-tolylsulfonyl)bicyclo[4.1.0]heptane (40a): IR (neat) v 1715, 1599, 1339, 3-azabicycl0[3.l.O]hexane (29a): IR (neat) v 1685, 1600, 1165 cm-'; 'H-NMR (CDC13) 6 0.55 (dd, J = 4.9, 9.3 Hz, 1H), 1340, 1160 cm-'; 'H-NMR (CDC13) 6 0.58 (dd, J = 5.5, 7.7 Hz, 0.66 (dd, J = 4.9, 5.4 Hz, 1 H), 0.85 (dddd, J = 1.6, 5.4, 8.0, 1 H), 0.71 (dd, J = 4.0, 5.5 Hz, 1 H), 1.33 (ddd, J = 3.7, 4.0, 9.3 Hz, 1 H), 1.84 (dddd, J = 1.6, 6.2, 9.8, 13.7 Hz, 1 H), 2.06 7.7 Hz, 1 H), 2.44 (s, 3 H), 3.00 (d, J = 9.2 Hz, 1 HI, 3.07 (d, (dddd, J = 4.0, 5.4, 8.0, 13.7 Hz, 1H), 2.09 (s, 3 H), 2.39 (s, 2 J = 17.0 Hz, 1 H), 3.14 (d, J = 17.0 Hz, 1 HI, 3.22 (dd, J = H),2.42(~,3H),2.53(ddd,J=5.4,9.8,11.7Hz,lH),2.75(d, 3.7,9.2 Hz, 1H), 3.53 (d, J = 9.2 Hz, 1H), 3.73 (d, J = 9.2 Hz, J = 11.7 Hz, 1H), 3.19 (ddd, J = 4.0, 6.2, 11.7 Hz, 1 H), 3.53 lH),7.32(d,J=8.2Hz,2H),7.46(d,J=8.0Hz,2H),7.52(d, J = 11.7 Hz, 1 H), 7.29 (d, J = 8.3 Hz, 2 H), 7.59 (d, J = 7.59 (m, 1 H), 7.68 (d, J = 8.2 Hz, 2 H), 7.85 (d, J = 8.0 Hz, 2 8.3 Hz, 2 H) I3C-NMR 6 207.1, 143.4, 139.9, 129.7, 127.5, 51.7, H); MS mlz 355 (M+),250,200,155,105(base peak), 91. Anal. 48.4,42.9, 30.2,23.4,21.5, 16.5, 16.2, 15.2; MS m l z 307 (M+), Calcd for C ~ ~ H Z ~ N O C,~67.58; S: H, 5.95; N, 3.94; S, 9.02. 164, 155, 152 (base peak), 91. Anal. Calcd for C I ~ H ~ I N O ~ S : Found: C, 67.45; H, 6.15; N, 3.78; S, 8.96. C, 62.51; H, 6.89; N, 4.56; S, 10.43. Found: C, 62.39; H, 6.95; Reaction of 14c with 28. The crude product, which was N, 4.45; S, 10.50. prepared from 14c (52.2 mg, 0.198 mmol) and 37 (77.7 mg, Reaction of 39b with 13a. The crude product, which was 0.238 mmol) in CH3CN (2.0 mL) at 70 C for 4 h followed by prepared from 39b (30 mg, 0.114 mmol) and 13a (36 mg, 0.137 treatment with 10% HC1, was purified by silica gel chromammol) in CH3CN (5.7 mL) at 70 "C for 4 h followed by tography (ethyl acetate-hexane, 1:6-1:3) t o give 29c (23.7 mg, treatment with [FeC12(DMF)31[FeC41(223mg, 0.41 mmol), was 32%), 30c (10.8 mg, 25%), and 31 (9.1 mg, 12%). rel-(IS,5S)-5-MethylI-(2-oxo-2-phenylethyl)-3-(p-tolyl- purified by silica gel chromatography (ethyl acetate-hexane, 1:2-1:l) to give 40b (13.9 mg, 40%). sulufonyl)-3-azabicyclo[3.1.Olhexane(29c): IR (Nujol) Y rel-(1R,6R)-6-(2-0xopropyl)-3-(p-tolylsulfonyl)-3-aza1686, 1598, 1344, 1164 cm-l; 'H-NMR (CDC13) 6 0.31 (d, J = bicyclo[4.1.O]heptane (40b): IR (neat) v 1715, 1598, 1340, 5.3 Hz, 1H), 0.87 (d, J = 5.3 Hz, 1HI, 1.11(s, 3 H), 2.44 (s, 3 1160 cm-I; 'H-NMR (CDC13) 6 0.47 (dd, J = 4.8, 8.8 Hz, 1H), H), 2.93 (d, J = 17.6 Hz, 1 H), 2.99 (d, J = 9.5 Hz, 1 H), 3.03 0.53 (dd, J = 4.8, 4.8 Hz, 1 H), 0.79 (dddd, J = 1.8, 4.4, 4.8, (d, J = 9.5 Hz, 1 H), 3.13 (d, J = 17.6 Hz, 1 HI, 3.57 (d, J = 8.8 Hz, 1H), 1.63 (ddd, J =4.4, 5.1, 13.9 Hz, 1H), 1.87 (ddd, 8.9 Hz, 1 H), 3.67 (d, J = 8.9 Hz, 1 HI, 7.32 (d, J = 8.3 Hz, 2 J = 5.9, 10.3, 13.9 Hz, 1H), 2.01 (s, 3 H), 2.08 (d, J = 16.9 Hz, H), 7.42-7.49 (m, 2 H), 7.53-7.60 (m, 1 H), 7.68 (d, J = 8.3 1H), 2.36 (s, 3 H), 2.47 (ddd, J =5.1, 10.3, 11.7 Hz, 1H), 2.49 Hz, 2 H), 7.88 (d, J = 8.7 Hz, 2 HI; MS m l z 369 (M+), 264, (d, J = 16.9 Hz, 1 H), 2.92 (dd, J = 4.4, 11.4 Hz, 1 H), 3.14 238, 214, 155, 105 (base peak), 91; HRMS ( m l z ) calcd for (dddd, J = 1.8,4.4, 5.9, 11.7 Hz, 1 H), 3.51 (d, J = 11.4 Hz, 1 C Z ~ H Z ~ N369.1399, O~S found 369.1411. treatment with [FeC12(DMF)3][FeC14](289 mg, 0.531 mmol), was purified by silica gel chromatography (ethyl acetatehexane, 1:3-1:2) to give 19 (25.6 mg, 62%) and 18h (3.5 mg, 6%). rel-(lR,5R,6S)-6-(4Methylphenyl)-7-oxo-l-(2-oxopropyl)3-@-tolylsulfonyl)-3-azabicyclo[3.2.0]heptane (18h): IR (Nujol) v 1782,1717,1597,1346,1163cm-l; 'H-NMR (CDC13) 6 1.73 (s, 3 H), 2.17 (d, J = 18.6 Hz, 1 H), 2.21 (s, 3 H), 2.32 (d, J = 18.6 Hz, 1 H), 2.41 (s, 3 H), 3.16 (brs, 1H), 3.21 (ddd,

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Enyne Metathesis

Organometallics, Vol. 14, No. 11, 1995 5061

treatment with [FeC12(DMF)3][FeC141(173 mg, 0.318 mmol), H), 7.24 (d, J = 8.4 Hz, 2 H), 7.55 (d, J = 8.4 Hz, 2 H); MS was purified by silica gel chromatography (ethyl acetatem l z 307 (M+),264, 250, 155, 152, 91, 43 (base peak). Anal. hexane, 1:4-1:2) to give 40d (3.9 mg, 15%). Calcd for C16H21N03S: C, 62.51; H, 6.89; N, 4.56. Found: C, 5-(2-Oxopropyl)-l-@-tolylsulfonyl)1,2,3,6-tetrahydro62.40; H, 6.88; N, 4.43. pyridine (40d): IR (neat) v 1715,1595,1340,1160 cm-'; 'HReaction of 39c with 13a. The crude product, which was NMR (CDC13)6 2.13 ( 8 , 3 H), 2.18-2.28 (m, 2 H), 2.43 (s, 3 prepared from 39c (40 mg, 0.124 mmol) and 13a (39 mg, 0.149 H), 3.08 (s, 2 H), 3.16 (t,J = 5.9 Hz, 2 H), 3.50 (d, J = 2.0 Hz, mmol) in CH3CN (1.2 mL) at 70 O C for 4 h followed by 2 H), 5.58 (brs, 1H), 7.32 (d, J = 8.1 Hz, 2 H), 7.67 (d, J = 8.1 treatment with [FeC12(DMF)3][FeC14](243 mg, 0.446 mmol), Hz, 2 H); MS m l z 293 (M+), 277, 250 (base peak),155, 138, was purified by silica gel chromatography (ethyl acetate~S found 91, 43; HRMS ( m l z ) calcd for C I ~ H I ~ N O293.1086, hexane, 1:2) to give 40c (24.7 mg, 55%). reZ-(1R,GR,7R)-?-(Methoxycarbony1)-1-(2-oxopropy1~-3-293.1113. (p-tolylsulfonyl)-3-azabicyclo[4.1.0lheptane( 4 0 ~ ) :mp 138-9 "C; IR (KBr) v 1715, 1595, 1340, 1160 cm-l; 'H-NMR Acknowledgment. This work was supported by the (CDC13)6 1.54 (ddd, J = 1.0,5.4, 8.3 Hz, 1H), 1.96 (dddd, J = Grant-in-Aid for Scientific Research on Priority Area of 1.0, 6.8, 11.7, 14.2 Hz, 1 H), 1.97 (d, J = 5.4 Hz, 1H), 2.08 (s, Reactive Organometallics No. 05236106 from the Min3 H), 2.11 (dddd, J = 3.4, 5.4, 8.3, 14.2 Hz, 1 H), 2.43 (s, 3 H), istry of Education, Science, and Culture of Japan and 2.50 (ddd, J = 5.4, 10.3, 11.7 Hz, 1 H), 2.67 (d, J = 11.7 Hz, 1 the Asahi Glass Foundation. H), 2.78 (d, J = 18.6 Hz, 1H), 2.91 (d, J = 18.6 Hz, 1H), 3.29 (dddd, J = 1.5, 3.4, 6.8, 10.3 Hz, 1 H), 3.65 (s, 3 H), 3.68 (dd, Supporting Information Available: Te& describing the J = 1.5, 11.7 Hz, 1H), 7.30 (d, J = 8.3 Hz, 2 H), 7.59 (d, J = preparation of the starting materials, 2-14d-h and 39a-d, 8.3 Hz, 2 H); MS m l z 365 (M+), 334, 332, 210, 155, 152, 91 and Schemes 15 and 16 (14 pages). This material is contained (base peak), 43. Anal. Calcd for C I ~ H ~ ~ N O S C,S59.16; : H, in many libraries on microfiche, immediately follows this 6.34; N, 3.83; S, 8.77. Found: C, 59.06; H, 6.37; N, 3.85; S, article in the microfilm version of the journal, and can be 8.68. ordered from the ACS; see any current masthead page for Reaction of 39d with 13a. The crude product, which was ordering information. prepared from 39d (30 mg, 0.088 mmol) and 13a (28 mg, 0.106 OM950374E mmol) in CH&N (4.4 mL) at 70 "C for 4 h followed by