Organometallics 1996,14, 1945-1953
1945
Nucleophilic and Electrophilic Allylation Reactions. Synthesis, Structure, and Ambiphilic Reactivity of (g3-Allyl)ruthenium(II) Complexes Teruyuki Kondo,* Hiroyuki Ono, Nobuya Satake, Take-aki Mitsudo, and Yoshihisa Watanabe" Division of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Sakyo-ku, Kyoto 606-01, Japan Received November 3, 1994@ Several (y3-allyl)ruthenium(II)complexes bearing carbon monoxide ligands can function
as both a nucleophile and a n electrophile, i.e., a s a n ambiphile. Namely, they smoothly react with both aldehydes and NaCH(C0OMe)z under extremely mild reaction conditions to give the corresponding allylated products in good to high yields. The higher valent (y3allyl)ruthenium(IV) complex, Cp*RuC12(y3-allyl) (Cp* = pentamethylcyclopentadienyl), is only electrophilic and unusually high regioselectivity of allylation of carbon and nitrogen nucleophiles can be attained.
Introduction Interest in y3-allyl transition-metal chemistry, particularly that of (y3-allyl)palladium, has undergone incredible growth over the last decade,l and a large number of y3-allyltransition-metal complexes have been prepared. However, the essence of (y3-allyl)palladiummediated functionalization is the activation of an allylic system to be attacked by only nucleophilic compounds. On the other hand, several y3-allyl transition-metal complexes such as Ni,2 Ti,3 and Mo4 show nucleophilic reactivity and react with electrophiles such as aldehydes and ketones, while other Mo complexes show electrophilic r e a ~ t i v i t y .Some ~ y3-allyl Ni6 and Fe7 complexes are reported to react with both nucleophiles such as alkenyltin6*or malonate7 and electrophiles such as alkyl The reaction of alkyl halides with the allylic compounds, however, proceeds via alkylation of the metallic centers forming (alkyl)(allyl)metal complexes, and successive reductive elimination gives the produ c t ~ . Thus, ~ , ~ the allyl ligands are not attacked by the electrophiles during the reaction. Consequently, no y3@Abstract published in Advance ACS Abstracts, March 15, 1995. (1)(a)Trost, B. M. Acc. Chem. Res. 1980,13,385.(b) Trost, B. M.; Verhoeven, T. R. In Comprehensive Organometallic Chemistry;Wilkinson, G., Stone, F. G. A., Abel, E. W., Eds.; Pergamon Press: Oxford, UK, 1982;Vol. 8,p 799.(c) Tsuji, J. Organic Synthesis with Palladium Compounds; Springer-Verlag: New York, 1980. (d) Heck, R. F. In Palladium Reagents in Organic Syntheses; Katritzky, A. R., MethCohn, O., Rees, C. W., Eds.; Academic Press: London, 1985;Chapter 5,p 117.(e) Godleski, S. A. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, UK, 1991;Vol. 4,p 585. (2)(a) Corey, E. J.; Semmelhack, M. F. J:Am. Chem. SOC.1967,89, 2755.(b) Hegedus, L.S.; Wagner, S. D.; Waterman, E. L.; S.-Hansen, K. J . Org. Chem. 1975,40,593. (3)Collins, S.; Dean, W. P.; Ward, D. G. Organometallics 1988,7, 2289. (4)(a) Faller, J . W.; Linebarrier, D. L. J . Am. Chem. SOC.1989,111, 1937.(b) Faller, J. W.; John, J. A.; Mazzieri, M. R. Tetrahedron Lett. 1989,30,1769. ( 5 ) (a) Faller, J. W.; Lambert, C.; Mazzieri, M. R. J . Organomet. Chem. 1990, 383, 161.(b) Trost, B. M.; Merlic, C. A. J . Am. Chem. SOC.1990,112,9590. ( 6 ) (a)Grisso, B. A,; Johnson, J. R.; Mackenzie, P. B. J . Am. Chem. (b) Johnson, J. R.; Tully, P. S.; Mackenzie, P. B.; SOC.1992,114,5160. Sabat, M. J . Am. Chem. SOC.1991,113,6172. (7)Itoh, K.; Nakanishi, S.; Ohtsuji, Y. J . Organomet. Chem., 1994, 473,215.
allyl ligand exhibits both electrophilic and nucleophilic behavior. If a y3-allylligand in a transition-metal complex can be applied not only as an electrophile but also as a nucleophile, the chemistry of y3-allyl complexes could be further developed in organic syntheses. In the last decade, palladium-catalyzed allylation of carbonyl compounds has been achieved, but the use of low-valent metals is essential for the transformation of allylic compounds to allylic metal compound^.^,^ In the course of our studies on ruthenium catalysis,1° we have succeeded in developing several novel ruthenium-catalyzed allylation reactions as illustrated in Scheme l.ll They were classified as a nucleophilic allylation and an electrophilic allylation. Thus, there exists the possibility that (q3-allyl)rutheniumcomplexes can alternately function as a nucleophile and an electrophile, Le., as an ambiphile, depending on the reactivity of the substrates. In order to investigate this novel reactivity of (y3-allyl)ruthenium complexes, we have tried to synthesize several (y3-allyl)ruthenium(II)and (8)(a) Trost, B. M.; Herndon, J. W. J . Am. Chem. SOC.1984,106, 5835. (b) Matsubara, S.; Wakamatsu, K.; Morizawa, Y.; Tsuboniwa, N.; Oshima, K.; Nozaki, H. Bull. Chem. SOC.Jpn. 1985,58, 1196.(c) Tabuchi, T.; Inanaga, J.; Yamaguchi, M. Tetrahedron Lett. 1986,27, 1195.(d) Tabuchi, T.; Inanaga, J.; Yamaguchi, M. Tetrahedron Lett. 1987,28,215. (e) Masuyama, Y.; Kinugawa, N.; Kurusu, Y. J . Org. Chem. 1987, 52, 3702. (0 Masuyama, Y.;Hayashi, R.; Otake, K.; Kurusu, Y. J . Chem. SOC.,Chem. Commun. 1988,44.(g) Takahara, J. P.; Masuyama, Y.; Kurusu, Y. J . Am. Chem. SOC.1992,114,2577.(h) Qiu, W.; Wang, Z. J . Chem. SOC.,Chem. Commun. 1989,356.(i) Zhang, P.; Zhang, W.; Zhang, T.; Wang, Z.; Zhou, W. J . Chem. SOC.,Chem. Commun. 1991,491. (9)Only one example showing that (n-ally1)palladium intermediate serves as a nucleophile rather than its normal reactivity as an electrophile without low-valent metal reductant was reported by Trost et al. in the reductive cleavage of enedicarbonates: Trost, B. M.; Tometzki, G. B. J . Org. Chem. 1988,53,915. (10)(a) Mitsudo, T.; Hori, Y.; Watanabe, Y. J . Organomet. Chem. 1987,334,157,and references cited therein. (b) Tsuji, Y.; Kotachi, S.; Huh, K.-T.; Watanabe, Y. J . Org. Chem. 1990,55,580, and references cited therein. (c)Kondo, T.; Akazome, M.; Tsuji, Y.; Watanabe, Y. J . Org. Chem. 1990,55,1286,and references cited therein. (11)(a)Tsuji, Y.; Mukai, T.; Kondo, T.; Watanabe, Y. J. Organomet. Chem. 1989,369,C51. (b) Kondo, T.; Mukai, T.; Watanabe, Y. J . O g . Chem. 1991, 56, 487. (c) Mitsudo, T.; Zhang, 2.-W.; Kondo, T.; Watanabe, Y. Tetrahedron Lett. 1992,33,341. (d) Mitsudo, T.; Zhang, S.-W.; Satake, N.; Kondo, T.; Watanabe, Y. Tetrahedron Lett. 1992, 33,5533. (e) Zhang, S.-W.; Mitsudo, T.; Kondo, T.; Watanabe, Y. J . Organomet. Chem. 1993,450,197.(0 Allylation reactions of trifluoromethyl ketones and aldoximes are our unpublished results.
0276-733319512314-1945$09.00/0 0 1995 American Chemical Society
Kondo et al.
1946 Organometallics, Vol. 14, No. 4, 1995 Scheme 1
F
R'
R
AU
R
T"
-
T
R
R
u NR2
-(IV)complexes which seem to be the most plausible key intermediates in our previously reported rutheniumcatalyzed allylation reactions.lla,e In this paper, we present details of the synthesis, structure, and ambiphilic reactivity of (y3-allyl)Ru(C0)&. In addition, a higher valent (y3-allyl)ruthenium(IV) complex reacted with only nucleophiles and a n unusually high regioselectivity of allylation of both carbon and nitrogen nucleophiles was attained. Results and Discussion Synthesis of (qS-allyl)RuL&(L = CO or PPhs, X = OCOR or O W . First, we tried to synthesize novel ruthenium complexes bearing both q3-allyl and carboxylate ligands by direct oxidative addition of allyl carboxylates to low-valent ruthenium complexes such as Ru3(C0)12 and Ru(COD)(COT)[(y4-1,5-cyclooctadiene)(y6-1,3,5-cyclooctatriene)rutheniuml. However, the reaction did not proceed even in refluxing toluene. Then, we employed the reaction of ruthenium halide with NaOAc.12 Fortunately, Pino et al. already reported the synthesis of (y3-C3H5)Ru(CO)3Br(la)from the reaction of Ru~(C0)12with allyl bromide.13 Although the complex l a did not react with NaOAc, the treatment of l a with AgOAc in dry CH2C12 a t room temperature for 15 h under an argon atmosphere in the dark afforded (y3C3H5)Ru(C0)30Ac (2a) as white needles in 44% yield (after purification by column chromatography (Al2O3, CH2Cl2) and recrystallization from n-pentane). Similarly, (y3-C3H5)Ru(C0)30COPh(2b) (40% yield), (y3-2methallyl)Ru(CO)3OAc (2c)(16% yield), and (q3-C3H5)Ru(CO)a(PPhs)OAc(2d)(6%)were synthesized (Scheme 2). Furthermore, [(y3-C3H5)Ru(C0)3]+(OTf)- (2e) was obtained in 47% yield from the reaction of l a with (12)For example, see: Young, R.; Wilkinson, G. Inorg. Synth. 1977, 17,79. (13)Sbrana, G.; Braca, G.; Piacenti, F.; Pino, P. J. Orgunomet. Chem. 1968, 13, 240.
Scheme 2 R 3.00a(T)) 1.84 0.05 1 0.052
'R = XIIF01 - IF4/XIFol. R, = [X.o(lF0/- ~Fc~)2/~.oFo211'2. Table 3. Bond Angles (deg) for 2a
ni
Figure 1. Molecular structure and labeling scheme for 2f. Table 2. Bond Lengths (A) for 2a Ru(l)-0(7) 2.167(3) R U ( ~ ) - C ( ~ )i.953(5) Ru(l)-C(4) 2.232(4) Ru(l)-C(6) 2.2370) S(1)-0(5) 1.433(4) S(l)-C(7) 1.805(6) F(2)-C(7) 1.291(7) O(l)-C(l) 1.1330) 0(3)-C(3) 1.130(5)
0(7)-H(7) 0.949(3) C(4)-H(1) 1.028(5) C(5)-C(6) 1.392(7) C(6)-H(4) 1. O W Ru(1)-C(1) 1.866(4) Ru(l)-C(3) 1.961(5) R U ( ~ ) - C ( ~ )2.226(4) S(1)-0(4) 1.422(4) S(1)-0(6) 1.41l(3)
F(l)-C(7) F(3)-C(7) 0(2)-c(2) 0(7)-H(6) C(4)-C(5) C(4)-H(2) c(5)-~(3) C(6)-H(5)
1.337(7) 1.312(7) 1.125(5) 0.946(3) 1.391(7) 0.950(5) 1.048(5) 0.9760)
and 1321 cm-' (vSp(coo))(KBr). The position and value of Av (vasp(coo)- v s p ( ~ ~ ~ # 2 ~is1quite 5 large (298 cm-l), revealing an UnsPmetrical monodentate (7') coordination mode of the acetat0 ligand to ruthenium.16 Furthemore, in the 13cNMR spectra,chemical shifi values (15)(a) Nakamoto, K. Infrared andRaman Spectra oflnorganic and Coordination Compounds;John Wiley C Sons: New York, 1978;p 232. (b) Dobson, A.;Robinson, S. D.; Uttley, M. Inorg. Synth. 1977,17,124.
0(7)-R~(l)-C( 1) 0(7)-R~(l)-C(4) C(l)-Ru(l)-C(2) C( 1)-Ru( 1)-C(5) C(2)-Ru(l)-C(4) C(3)-Ru(l)-C(4) C(4)-Ru(l)-C(5) 0(4)-S(1)-0(5) 0(5)-S(1)-0(6) R~(l)-0(7)-H(6) Ru(l)-C(l)-O(l) Ru(l)-C(4)-C(5) C(5)-C(4)-H( 1) Ru(l)-C(5)-C(4) C(4)-C(5)-C(6) Ru(l)-C(6)-C(5) C(5)-C(6)-H(4) S(l)-C(7)-F( 1) F( l)-C(7)-F(2) 0(7)-Ru(l)-C(2) 0(7)-R~(l)-C(5) C(l)-Ru(l)-C(3) C(l)-Ru(l)-C(6) C(2)-Ru(l)-C(5) C(3)-Ru( 1)-C(5) C(4)-Ru(l)-C(6) 0(4)-S(1)-0(6) 0(5)-S(l)-C(7) Ru(l)-0(7)-H(7)
179.0(2) 82.2(1) 89.8(2) 83.4(2) 95.6(2) 161.4(2) 36.4(2) 114.1(2) 113.2(2) 112.1(2) 177.1(4) 71.6(3) 11734) 72.1(3) 122.0(4) 71.4(3) 122.8(5) 109.3(4) 106.6(6) 90.5(2) 97.1(1) 90.0(2) 97.4(2) 128.4(2) 130.0(2) 66.0(2) 116.9(3) 102.8(3) 111.2(2)
Ru( l)-C(2)-0(2) Ru(l)-C(4)-H(l) C(5)-C(4)-H(2) Ru( l)-C(5)-C(6) C(4)-C(5)-H(3) Ru( l)-C(6)-H(4) C(5)-C(6)-H(5) S(l)-C(7)-F(2) F(l)-C(7)-F(3) 0(7)-R~(l)-C(3) 0(7)-Ru(l)-C(6) C(l)-Ru(l)-C(4) C(~)-RU(1)-C(3) C(2)-Ru(l)-C(6) C(3)-Ru(l)-C(6) C(5)-Ru(l)-C(6) 0(4)-S( 1)-C(7) 0(6)-S( 1)-C(7) H(6)-0(7)-H(7) Ru(l)-C(3)-0(3) Ru(l)-C(4)-H(2) H(l)-C(4)-H(2) Ru(l)-C(5)-H(3) C(6)-C(5)-H(3) Ru( 1)-C(6) -H(5) H(4)-C(6)-H(5) S(l)-C(7)-F(3) F(2)-C(7)-F(3)
176.6(4) 120.5(3) 115.8(5) 72.3(3) 115.4(5) 117.5(4) 125.2(5) 112.2(4) 107.8(5) 89.0(2) 82.6(1) 98.7(2) 100.9(2) 161.0(2) 96.7(2) 36.4(2) 103.8(3) 103.8(3) 105.1(3) 177.1(4) 98.2(3) 121.2(5) 111.0(3) 119.5(5) 97.9(3) 109.9(5) 110.8(5) 110.0(6)
of the carbonyl "-on of carboxylate ligand of 2a-d were a t -170 ppm, which are higher than those of bidentate (v2) chelate carboxylato ligands.17 As for the ' H NMR of 2a,central, syn- and anti-H of v3-allyl ligand were observed at 6 5.19, 4.02, and 2.38 ppm, respectively. It has already been reported that (v3-C3H5)M(C0)3Br(M = Fe or Ru) exists in solution in a conformational equilibrium between endo and ex0 (16)For bidentate chelate (carboxy1ato)ruthenium complexes, see: (a) RuH(PPhs)s(OAc),Av = 75 cm-1. Rose, D.; Gilbert, J. D.; Richardson, R. P.; Wilkinson, G. J.Chem. SOC.A 1969,2610.(b) Ru[(S)-BINAPl(OAc)n, Av = 66 cm-'. O h , T.;Takaya, H.; Noyon, R. I n o g . Chem. 1988,27, 566. For monodentate (carboxy1ato)ruthenium complexes, see: (c) Ru(CO)z(PPh3)2(OAc)n,Av = 289 cm-l. Robinson, S.D.; Uttley, M. F. J. Chem. SOC.,Dalton Trans. 1973,1912. (17)For example, the chemical shift value (l3C NMR) of CH3COO in Ru[(S)-BINAPI(OAc)2 is 6 188.1
Kondo et al.
1948 Organometallics, Vol. 14, No. 4, 1995 Scheme 4
OC-
oc'
RU -0COR'
"to
Figure 2.
5
4
[Rul= Cp*RuCI(COD) Cp"RuBr(C0D) [Cp*RuOMel2 [Cp*RuCld2
84 84
83 83
: : : :
Scheme 5
16 16 17 17
overall yield99 % 99% 99% 99%
r.t., 16 h
Cp'RuCNcod)
t
Ph-CI
in THF
recrystallization
ph&
/
Figure 3. Molecular structure and labeling scheme for 3a. Scheme 3 3a, 47 % OC-dy
-Br
oc'
"to
endo ( > 9 5 5%)
-
Table 4. Bond Lengths (A) for 3a
OC-du-Br
oc'
''to exo
isomers differing principally in the orientation of the allyl group (Scheme 3).l4JSAt room temperature, the two isomers interconvert slowly (t1/2 > 10 min) and the endo isomer predominates (>95%). So, on the basis of lH NMR spectra and the structure of 2f, we confirmed that the present y3-allylruthenium complexes (2a-d) exist as the endo isomers. Consequently, the structure of these novel y3-allylruthenium carboxylate complexes (2a-d) is depicted as Figure 2. Synthesis of Cp*RuC12(q3-CH&HCH). We have already reported Ru(COD)(COT)-catalyzed regioselective allylation of carbonucleophiles.loe Recently, we found that the regioselective allylation of nitrogen nucleophiles was more effectively promoted by Cp*Ru catalysts at 0 "C within 1 h (Scheme 4).19 These products are obtained by selective y-attack of a nitrogen nucleophile to the (y3-allyl)ruthenium(IV)intermediate. Here, we synthesized a model complex of the reaction intermediate Cp*RuC12(y3-CHzCHCHPh)(3a)by direct oxidative addition of cinnamyl chloride to Cp*RuCl(COD). The complex 3a was obtained as red-brown crystals in 69% yield a h r recrystallization from CHC13Et20 (Scheme 5). The results of X-ray diffraction analysis for 3a are shown in Figure 3 and Tables 1 , 4 and 5. The complex 3a has a square-pyramidal structure with two chlorine atoms and the terminal carbons of the endo-y3-allyl ligand a t basal positions, similar to the reported C~*RUB~Z(~~-C~H~).~~ Reactivity of (q3-CsHs)Ru(CO)& ( l a , 2a, 2e). (i) Nucleophilic Allylation of Aldehydes with (q3-
Ru(l)-C1(1) Ru(1)-C(1) Ru(l)-C(3) Ru(l)-C(ll) Ru(l)-C(13) C(l)-C(2) C(3)-C(4) C(4)-C(9) C(6)-C(7) C(8)-C(9)
2.398(3) 2.18(1) 2.35(2) 2.25(1) 2.20(1) 1.38(2) 1.49(2) 1.38(2) 1.39(3) 1.45(2)
C(lO)-C(14) C(l1)-C(12) C(12)-C(13) C(13)-C(14) C(14)-C(19) Ru(l)-C1(2) Ru(l)-C(2) Ru(l)-C(lO) Ru(l)-C(12) Ru(1)-C(14)
1.45(2) 1.41(2) 1.46(2) 1.45(2) 1.48(2) 2.423(4) 2.14(2) 2.32(1) 2.16(1) 2.25(1)
C(2)-C(3) C(4)-C(5) C(5)-C(6) C(7)-C(8) C(lO)-C(ll) C(lO)-C(15) C(ll)-C(16) C(12)-C(17) C(13)-C(18)
1.43(2) 1.48(2) 1.43(2) 1.43(3) 1.46(2) 1.48(2) 1.53(2) 1.56(2) 1.50(2)
CsHs)Ru(CO)& Since the complexes la and 2a are thought to be the most plausible key intermediates in ruthenium-catalyzed allylation reactions of aldehydes with allylic acetateslla and allylic bromides, the reactivity of the complexes (la, 2a, 2e) toward several aldehydes was investigated. These complexes smoothly reacted with both aromatic and aliphatic aldehydes in the presence of Et3N in CHCL at room temperature for 48-72 h under an argon atmosphere, affording the corresponding homoallyl alcohols in 46- 70% yields (Scheme 6). Carbon monoxide, which was essential for the catalytic allylation of aldehyde,lla was not crucial for the present stoichiometric reaction. In the reaction with aliphatic aldehydes such as 1-hexanal and cyclohexanecarboxaldehyde, better results were obtained from 2a than from la. In both the catalytic and stoichiometric allylation of aldehydes, addition of amines such as Et3N is essential for both high catalytic activity and high yields of the products. It is considered that the added amine operates as a n hydrogen source as well as a suitable ligand for an active ruthenium intermediate. Without Et3N, the yield of 1-phenyl-3-buten-1-01from the reaction of la with benzaldehyde drastically decreased to 28%, together with the generation of a considerable amount of a yellow precipitate. This yellow solid would be the
(18)For M = Fe: Simon, F. E.; Lauher, J. W. Inorg. Chem. 1960, 19, 2338.
(19)Mitsudo, T.; Satake, N.; Kondo, T.; Watanabe, Y., unpublished results.
(20) Nagashima, H.; Mukai, K.; Shiota, Y.; Yamaguchi, K.; h a , K.; Fukahori, T.; Suzuki, H.; Akita, M.; Moro-oka, Y.; Itoh, K. Organometallics 1990, 9, 799.
Nucleophilic and Electrophilic Allylation Reactions
Organometallics, Vol. 14, No. 4, 1995 1949
Table 5. Bond Angles (deg) for 3a C1(l)-Ru( 1)-C1(2) C1( 1)-Ru( 1)-C(3) Cl( 1)-Ru( 1)-C( 12) C1(2)-Ru(l)-C( 1) C1(2)-Ru(l)-C( 10) C1(2)-Ru( 1)-C( 13) C( l)-Ru(l)-C(3) C( l)-Ru(l)-C( 12) C(2)-Ru(l)-C(3) C(2)-Ru( 1)-C( 12) C(3)-Ru(l)-C( 10) C(3)-Ru(l)-C( 13) C( 10)-Ru( 1) -C( 12) C(ll)-Ru(l)-C(12) C( 12)-Ru( 1)-C( 13) Ru( 1)-C( 1)-C(2) C(l)-C(2)-C(3) C(2)-C(3)-C(4) C(5)-C(4)-C(9) C(6)-C(7)-C(8) Ru( 1)-C( lO)-C( 11) C(ll)-C(lO)-C(l4) Ru( 1)-C( 11)-C( 10) c(lo)-c(ll)-c(l2) R~(l)-C(l2)-C(ll) C(l l)-C(l2)-C(13) Ru( l)-C(13)-C( 12) C( 12)-c(13)-c( 14) Ru( 1)-C( 14)-C( IO) C(lO)-C( 14)-c( 13) C1( 1)-Ru(l)-C( 1) Cl(l)-Ru(l)-C( 10) C1(l)-Ru( 1)-C( 13) C1(2)-Ru( 1)-C(2) C1(2)-Ru(l)-C(ll) C1(2)-Ru( 1)-C( 14) C(1)-Ru(1)-C( 10) C(l)-Ru(l)-C( 13) C(2)-Ru( 1)-C( 10) C(2)-Ru(l)-C( 13) C(3)-Ru( 1)-C( 11) C(3)-Ru( 1)-C( 14) C( 10)-Ru( 1)-C( 13) C(ll)-Ru(l)-C(13) C(12)-Ru( 1)-C( 14)
83.9(1) 84.9(4) 140.5(6) 80.2(5) 112.8(4) 128.4(3) 64.1(5) 92.0(7) 36.7(6) 127.8(8) 118.8(5) 91.6(5) 62.0(7) 37.1(6) 39.2(5) 69.6(9) 118(1) 129(1) 123(1) 121(1) 68.9(7) 107(1) 74.0(7) 107(1) 75.1(9) llO(1) 68.8(7) 105(1) 74.3(8) 108(1) 125.3(4) 83.9(4) 13934) 90.5(5) 83.7(3) 146.4(3) 150.0(5) 88.0(5) 155.5(6) 109.3(6) 150.7(5) 88.2(5) 62.6(5) 63.7(4) 63.7(6)
Ru( l)-C(2)-C(l) Ru( 1)-C(3)-C(2) C(3)-C(4)-C(5) C(4)-C(5)-C(6) C(7)-C(8)-C(9) Ru( 1)-C( 10)-C( 14) c(ll)-c(lo)-c(l5) Ru( 1)-C( 11)-C( 12) C( lO)-C( 11)-C( 16) Ru( 1)-C( 12)-C( 13) C(ll)-C(12)-C(l7) Ru( 1)-C( 13)-C( 14) C( 12)-C( 13)-C( 18) Ru(1)-C( 14)-C( 13) C( lO)-C( 14)-c( 19) C1( 1)-Ru( 1)-C(2) CI(l)-Ru(l)-C(ll) C1( 1)-Ru( 1)-C(14) C1(2)-Ru( 1)-C(3) C1(2)-Ru( 1)-C( 12) C( 1)-Ru( 1)-C(2) C( 1)-Ru( 1)-C( 11) C( l)-Ru( 1)-C( 14) C(2)-Ru(l)-C(ll) C(2)-Ru( 1)-C( 14) C(3)-Ru( 1)-C( 12) C(1O)-Ru(1)-C(l1) C( 10)-Ru( 1)-C( 14) C(1 l)-Ru(l)-C(14) C( 13)-Ru( l)-C( 14) Ru( l)-C(2)-C(3) Ru( 1)-C(3)-C(4) C(3)-C(4)-C(9) C(5)-C(6)-C(7) C(4)-C(9)-C(8) Ru(1)-C( 10)-C(15) C( 14)-c( lO)-C( 15) R~(l)-C(ll)-C(l6) C(12)-C(ll)-C(16) Ru( 1)-C( 12)-C( 17) c(13)-c( 12)-c(17) Ru(1)-C( 13)-C( 18) C( 14)-c( 13)-c( 18) Ru(l)-C(14)-C( 19) C(13)-C(14)-C( 19)
Scheme 6 ((RU(C0)3X
+
PhCHO
r,t., 65-72 h
EbN, in CHC13
-
Scheme 7 73.2( 10) 63(1) 118(1) 116(1) 119(1) 68.8(7) 127(1) 67.8(8) 123(1) 72.0(8) 124(1) 72.7(7) 127(1) 69.2(7) 123(1) 91.6(5) 103.3(3) 101.4(4) 125.4(4) 91.0(5) 37.2(6) 126.0(5) 120.0(5) 163.3(6) 122.1(6) 127.9(6) 37.1(5) 36.9(5) 62.8(4) 38.1(5) 7% 1) 124.9(10) 117(1) 120(1) 117(1) 127(1) 124(1) 127.7(9) 128(1) 123(1) 125(1) 131.0(9) 125(1) 129(1) 127(1)
Ph
l a ; X-Br 2a; X-OAc 2e; X=OTf
70 %
66% 62% r.t., 48 h
((Ru(C0)aX
+ n-C$illCHO
c
EbN, in CHC13
l a ; X=Br 2a; X=OAc
n-C5H11
60% 67 %
OH r.t, 48 h ((RU(CO)3X + O C H O l a ; X=Br 2a; X=OAc
EbN, in CHC13
46% 67 %
halogen-bridged (homoallyla1koxy)rutheniumcluster,21 since the hydrogen source for the generation of the homoallyl alcohol is extremely deficient. Other hydrogen sources such as methanol were also examined in the reaction, but the yield of the homoallyl alcohol did (21) 13C NMR of this complex (THF-da): 6 44.35 (CHz),73.27 (CH), 78.51 (C), 115.62 ( = C H 2 ) , 125.74-128.53 (-CH and phenyl), 145.99 (phenyl CI), 183.50, 184.36, 189.28 (M - CO).
I
C&H&HO
+ EbN
i n ~ b o r C ~ ~ l *3
1
?H
Br in CHCl3
Ph
+ C&+(CD&
D content: 9.2 %
+ Et~N-dls
12 %
Scheme 8 PhCHO
+
cat. RUJ(CO)~~ Et3N-C0 *
-0Ac
L
Ph
~
55%
+
Ph+
45%
(overall yield = 64 %)
not increase (-40%). So, we examined the following deuterium-labeled experiments in the stoichiometric allylation of benzaldehyde with la (Scheme 7). In C6D6 or CDCl3, no deuterium was detected in the homoallyl alcohol. Even with the use of C6H&DO or CsD&DO, no deuterium was incorporated into the hydroxy group of the product, but when C6H5N(CD& or Et3N-dls was used in place of Et3N in CHCls, deuterium was incorporated into the hydroxy group of the generated homoallyl alcohol a t 9.2% and 12%,respectively. These results strongly suggest that the hydrogen source of the homoallyl alcohol is not the solvent (or aldehyde), but the amine. It is well-known that ruthenium complexes showed high catalytic activity for the transalkylation reaction between tertiary amines.22 In the present reaction, a similar hydride abstraction from tertiary amines by the ruthenium complex would occur via a metallaazacyclopropane or an iminium ion intermediate. As for la, dynamic n-u (r3-r1)equilibrium of the allyl ligand could not be observed by lH NMR (room temperature to 80 "C in toluene-&). The reaction of la with benzaldehyde was monitored by lH NMR. During the reaction, such n-u isomerization could not be observed and direct insertion of the carbonyl group into the y3-allyl-Ru bond occurred. In consideration of these results, the possibility that ~ t - uisomerization of the allyl ligand in la causes the high nucleophilicity of la toward aldehydes was excluded.23 In addition, it is suggested by preliminary MO calculation that the conversion of n to u of the allyl ligand in ruthenium is thermodynamically more unfavorable than that of palladi~m.~~ Thus, on the basis of the results mentioned above, we present the most plausible pathway to homoallyl alco(22)Wilson, R. B.; Laine, R. M. J.Am. Chem. SOC.1985, 107, 361. (23) If the present reaction proceeds via a (u-ally1)ruthenium intermediate, high diastereoselectivity (anti selectivity) of the allylation reaction using crotyl (or l-methylallyl) acetate can be expected through a six-membered cyclic transition ~ t a t e . ~However, .~g under the catalytic reaction conditions, low diastereoselectivity was observed (Scheme 8). (24)The energy gap between the model complexes, [Ru(NH3)(C0)3(a3-C3Hs)l+and [RU(NH~)(CO)~(~~-C~H~)I, was calculated as -26 kcall mol by an ab initio MO/MP4 (SDQ) method, which is larger than that between Pd(CO)z(q3-C3Hs)and P ~ ( C O ) Z ( ~ ' - C(-23 ~ H ~kcaVmo1): ) Sakaki, S., unpublished result.
Kondo et al.
1950 Organometallics, Vol. 14, No. 4, 1995
Scheme 10
Scheme 9
(( RuCO)JX + la; X=Br 2a; X=OAC 2e; X=OTf
NaCH(C02Md2
r.t., 24-40h ~~THF
’
h
C
H(C02Me)2
55% 32% 37% I
in C0& hols by the reaction of 73-allylruthenium(II)complexes 38 with aldehydes in the presence of amines. Direct insertion of the carbonyl group of a n aldehyde to the 73-allyl-ruthenium bond (not through a yl-allylruthenium complex) gives a (homoallyla1koxy)ruthenium intermediate. We now suggest that a-hydride transfer from amine to the ruthenium produces a (homoallyla5 (18 %) 4 (82 %) lkoxy)(hydrido)ruthenium complex, which then undergoes reductive elimination of the observed homoallyl (overall yield = 92 %) alcohol product. (ii) Electrophilic Allylation of NaCH(COdMe)2 Scheme 11 with (q3-allyl)Ru(CO)~ (la, 2a, 2e). As mentioned Ph previously, we had found that several ruthenium complexes showed high catalytic activity for regioselective allylation of carbonucleophiles. lie Therefore we investigated the reactivity of (q3-allyl)Ru(C0)& (la,2a, 2e) toward a representative carbonucleophile, NaCH(C0238 Meh. Results are shown in Scheme 9. (73-Allyl)Ru(C0)&, r.t, 2 h p h d la, 2a and 2e, smoothly reacted with NaCH(COOMe)2 in THF a t room temperature for 24-40 h under a n argon atmosphere to give the corresponding allylated products in 32%-55% yields. It is noteworthy that the 6 (82 %) same complex showed reverse reactivity, depending on the reactivity of the opposing substrates. The role of the carbonyl ligand is highly important, octadiene and N-methylpiperidine. The complete conand the ambiphilic reactivity is realized only in rutheversion of the complex 3a required 2 h, and only nium complexes bearing carbon monoxide ligands. branched product 6 was obtained selectively in 82% Since we discovered the ambiphilic reactivity of (q3yield (Scheme 11). The present reaction did not proceed allyl)ruthenium(II) complexes,25several research groups in the absence of N-methylpiperidine, and such base is in Japan prepared phosphine-coordinated (y3-allyl)required for the elimination of HC1 from acetylacetone ruthenium(I1) complexes. However, these ruthenium and 3a. complexes, such as ( v ~ - C ~ H ~ ) R U ( P M and~ ~(v3) B ~ ~ ~ The results of these stoichiometric reactions are in C ~ H ~ ) R U ( P E ~ ~ ) ~ could C O Cnot F ~react , ~ ~ with NaCHaccord with those of the catalytic reactions depicted in (C02Me)2, while they reacted with benzaldehyde only Scheme 4. In addition, complex 3a showed high cataat elevated temperature (50-80 “C) to give the correlytic activity in the allylation of both carbon and sponding homoallyl alcohol. nitrogen nucleophiles. Hence, it appears that the active (iii) Regioselective Electrophilic Allylation of intermediate in the Cp*Ru complex-catalyzed allylation Carbon and Nitrogen Nucleophiles with Cp*RuClzof nucleophilesohas configuration analogous to complex (q3-allyl).The reaction of Cp*RuC12(v3-CH2CHCHPh) 3a. Although h e r m a r k et al. reported the regiocontrol (3a) with 2 equiv of piperidine in the presence of 1.2 of alkylation28 and a m i n a t i ~ nof~ y3-allylpalladium ~ equiv of 1,5-cyclooctadiene in CD2C12 a t room tempersystems, the regioselectivity is not always high. Furature was monitored by lH NMR. The complex 3a was ther, addition of p h o ~ p h i n eor~ other ~ ~ , ~specific ~ ligandBb completely consumed in 20 min to give the correspondis necessary to promote their reactions. ing allylamines 4 and 5 (the ratio was 82:18) in total In addition, Cp*RuCl(COD)-catalyzed allylation of 92% yield (Scheme 10). Without 1,5-cyclooctadiene, the piperidine with other allylic carbonates also afforded the ratio of 4 and 5 was 62:38 under the same reaction branched N-allylamines as a major product (Table 6). conditions after 10 min. Furthermore, complete isomerThe reaction mechanism is not clear yet, but at this ization of 4 to 5 proceeded and only linear allylamine 5 stage, we consider that it is difficult for secondary amine was obtained after 2 h. Thus, 1,5-cyclooctadiene plays to preferentially attack the more sterically hindered the role of the ligand that suppresses the isomerization allyl carbon directly. In consideration of the result that of 4 to 5. the ruthenium complexes also catalyze the isomerizaWe examined the reaction of 3a with 3 equiv of tion of the generated branched amine 4 to the linear acetylacetone in the presence of 1.2 equiv of 1,5-cycloamine 5 (vide supra), the amine nucleophilically sub-
,
(25)Kondo, T.;Ono, H.; Mitsudo, T.; Watanabe, Y. The 39th Symposium on Organometallic Chemistry, Japan: Tokyo (Japan), October 1992;Abstr. p 199. (26)Maruyama, Y.; Shimizu, I.; Yamamoto, A. Chem. Lett. 1994, 1041.
(27)Komiya, S.;Kabasawa, T.; Yamashita, K.; Hirano, M.; Fukuoka, A. J. Organomet. Chem. 1994, 471, C6.
~
~~~
(28)(a) h e r m a r k , B.;Hansson, S.; Krakenberger, B.; Vitagliano, A,; Zetterberg, K. Organometallics 1984,3, 679.(b) Sjagren, M. P. T.; Hansson, S.; h e r m a r k , B. Organometallics 1994, 13, 1963, and references cited therein. (29)h e r m a r k , B.; h e r m a r k , G.; Hegedus, L. S.; Zetterberg, K. J. Am. Chem. SOC.1981, 103, 3037.
Nucleophilic and Electrophilic Allylation Reactions
Organometallics, Vol. 14, No. 4, 1995 1951
Table 6. Cp*RuCl(COD)-CatalyzedAllylation of Piperidine with Allylic Methyl Carbonate@ entry 1
allylic carbonate Ph&OC02Me
yield (70)
productsh(ratio)
99
0
Ph&N
9
(84:16)
P
h
p
98
(9O:lO)
OC02Me
3 YOC02Me -
14
4
91
(7426)
-0COZMe
(56:44)
Standard conditions: Cp*RuCl(COD) (0.10 mmol), allylic carbonate (2.5 mmol), piperidine (2.5 mmol), and THF (5.0 mL) at 0°C for 1 h under AI. Determined by GLC.
stitutes the chlorine ligand to give the intermediates 7 and 8 (Scheme 12). A cis-reductive elimination from the intermediate 7 would give 4, while 5 would be generated from 8. We suggest two reasons for the kinetic advantage on the formation of the intermediate 7: (1) A nucleophile is liable to substitute Cl(1) compared with Cl(2) on the basis of the distances between atoms in 3a (C(3)-C1(1)(3.21 A) > C(l)-C1(2)(2.97 A) and/or RuC(3X2.35 A) > Ru-C(1)-(2.18 A)). (2) The elimination of Cl(1) from 3a is accelerated more than that of Cl(2) by the steric hindrance of hydrogen atoms on the phenyl group. Hence, in the present reaction, the intermediate 7 is predominantly generated to give the branched product 4, s e l e ~ t i v e l y . ~ ~
Conclusion Although "ambiphilic" reagents are useful for reactions involving the sequential formation of two bonds and several efficient carbocycle-forming reactions have been developed, ambiphilic reagents so far reported are zwitterionic and they are usually employed in the twostep cyclization reactions-first as a nucleophile and then as an e l e ~ t r o p h i l e . ~ ~ We have now succeeded in the synthesis of the first (v3-allyl)ruthenium(II) carboxylates and triflate and disclosed that v3-allylligands in these complexes as well as (r3-C3H~)Ru(C0)3Br show a real ambiphilic reactivity. Namely, v3-allyl ligands of the present (y3-allyl)ruthenium(I1) complexes can function as both a nucleophile and an electrophile in the individual reactions, depending on the reactivity of the opposing substrate^.^^ (30) In considering the regioselectivity, several contributing factors must be weighed. These factors include (1)the steric hindrance of the regioisomeric alkylation sites, (2) the reactivity of the nucleophile, (3) the steric hindrance of the nucleophile, (4) the charge distribution in the q3-allyl complex, and (5) the relative stability of the two possible metal-olefin complexes. If the three carbons of the allylic fragment and the substituent are approximately in a single plane so that the steric hindrance to attack a t the more substituted allylic carbon is minimized, charge effects dominate. In the present reaction, this charge control may be expected to give the kinetic product 4 whereas equilibration may be expected to give the thermodynamically preferred, less hindered, more fully conjugated product 5. (31)Hegedus, L. S.; Holden, M. S. J. Org. Chem. 1986, 50, 3920, and references cited therein. (32) Ambiphilic behavior in (CO)SW=NPh has been recently reported: Amdtsen, B. A.; Sleiman, H. F.; Chang, A. K.; McElwee-White, L. J. Am. Chem. SOC.1991, 113, 4871.
Further, we succeeded in developing the regioselective allylation of nucleophiles which is characteristic of Cp*Ru catalysts. We anticipate that this novel reactivity of (v3-allyl)ruthenium complexes will be applicable as a useful reagent and catalyst to synthetic organic chemistry.
Experimental Section General Considerations. All manipulations were performed using a Schlenk technique. 'H (270.05 MHz) and l3C NMR spectra (67.80 MHz) were measured on a JEOL GSX270 spectrometer. Samples were dissolved in CDC13 or THFd8, and the chemical shift values were expressed relative to Me4Si as an internal standard. IR spectra were recorded on a Shimadzu FT-IR 8100 spectrophotometer. GLC analyses were carried out on a Shimadzu GC-14A chromatograph equipped with capillary columns (Shimadzu capillary column: 3 mm i.d. x 50 m; CBPlO-S25-050 (polarity similar to OV-1701) and CBP20-S25-050 (polarity similar to PEG-2OM)). Mass spectra (MS) were obtained on a Shimadzu QP-2000 spectrometer. Melting points of the ruthenium complexes were measured on a Yanagimoto micro-melting-point apparatus. Elemental analyses were carried out at the Microanalytical Center of Kyoto University. Authentic samples of 1-phenyl-3-buten-1-01, 1-nonen-4-01, and l-cyclohexyl-3buten-1-01 were synthesized by the method in the literature33 and distilled (>98% purity by GC). Dimethyl 2-propenylmalonate was synthesized by palladium-catalyzed allylation of dimethyl malonate with allyl methyl carbonate.34 Materials. Solvents were distilled from suitable drying reagents under an argon atmosphere just before use. Silver acetate, silver benzoate and silver triflate were purchased from Aldrich Chemical Co. and used without further purification. R u ~ ( C O ) was ~ P purchased from Strem Chemicals and used without further purification. (v3-C3H5)Ru(C0)3Br(la)13and (y3-C3H5)Ru(CO)2(PPh3)Br (112)~~ were prepared by the methods in the literatures. 2-Methallyl bromide used in the preparation of (q3-2-methallyl)Ru(C0)3Br(lb) was prepared by halogen exchange reaction of 2-methallyl chloride with L i B P and used after distillation (>go% purity by GC). PhN(CD& was prepared by ruthenium-catalyzed N-alkylation of aniline with CDSOD.~'Et3N-d15 (D, 98%) was purchased from Cambridge Isotope Laboratories and used without purification. Cp*RuCl(COD),38C ~ * R U B ~ ( C O [DC) ,~~*~R U O M and ~ I ~[ ,C~p~* R u C l ~ l ~ ~ ~ were prepared according to the literature methods. Preparation of (p3-2-Methallyl)Ru(CO)3Br(lb). The complex l b was prepared from RuB(CO)~:! and 2-methallyl bromide by a procedure similar to that for la.13 mp: 107110 "C. Anal. Calcd for C7H703BrRu: C, 26.27; H, 2.20. Found: C, 25.77; H, 2.16. 'H NMR (CDC13): 6 2.08 (3H, s, CH3), 3.05 (2H, s, CHH (anti)),3.93 (2H, s, CHH (syn)). 13C NMR (CDC13): 6 25.59 (CH3), 59.16 (CH21, 128.60 ((CH2)C(CH3)), 188.96 and 191.10 (M - CO). Preparation of (q3-Allyl)RuL& Treatment of the complex l a (605 mg, 1.98 mmol) with silver acetate (331 mg, 1.98 mmol) in CH2Cl2 (30 mL) a t room temperature for 15 h under an argon atmosphere in the dark affords a colorless solution and brown precipitate. The colorless solution was chromato(33)(a) Mukaiyama, T.; Harada, T. Chem. Lett. 1981, 1527. (b) Nokami, J.; Otera, J.;Sudo, T.; Okawara, R. Organometallics 1983,2, 191. (34) Tsuji, J.; Shimizu, I.; Minami, I.; Ohashi, Y.; Sugita, T.; Takahashi, K. J . Org. Chem. 1986,50, 1523. (35) Sbrana, G.; Braca, G.; Benedetti, E. J . Chem. Soc., Dalton Trans. 1975, 754. (36) Semmelhack, F.; Helquist, P. M. Organic Syntheses; Wiley: New York, 1988; Collect. Vol. VI, p 722. (37) Huh, K.-T.; Tsuji, Y.; Kobayashi, M.; Okuda, F.; Watanabe, Y. Chem. Lett. 1988, 449. (38) Oshima, N.; Suzuki, H.; Moro-oka, Y. Chem. Lett. 1984, 1161. (39)Albers, A. 0.; Robinson, J. D.; Shaver, A,; Singleton, E. Organometallics 1986, 5, 2199. (40) Koelle, U.; Kossakowski, J. J . Organomet. Chem. 1989, 362, 383.
Kondo et al.
1952 Organometallics, Vol. 14, No. 4, 1995
Scheme 12
3a
I
5
8
graphed on neutral A 1 2 0 3 (2 cm i.d. x 2 cm; eluent CHZClz), and solvent was removed under vacuum. The resulting white solid was dissolved in a small amount of n-pentane and cooled at --40 "C for recrystallization. White needles of 2a were obtained (247 mg, 44%). mp: 33-35 "C. Anal. Calcd for CgHeO5Ru: C, 33.68; H, 2.83. Found: C, 33.61; H, 2.85. IR data (KBr): 2110, 2062,2014 (v(coJ, 1619 (V(COO)aaym) and 1321 (V(COO)~,,J cm-l. 'H NMR (CDC13) 6 1.79 (3H, s, CHd, 2.38 (2H, d, J = 12.86 Hz, CHH (anti)),4.02 (2H, d, J = 7.92 Hz, CHH (syn)), 5.19 (lH, m, CH). 13C NMR (CDC13): 6 22.63 (CH3), 60.73 (CHz), 108.20 (CH),176.00 (CH&OO), 190.00 and 192.40 (M - CO). Complex 2b was obtained by the reaction of l a (605 mg, 1.98 mmol) with silver benzoate (457 mg, 2.00 mmol) in CHZClz (30 mL) at room temperature for 24 h, as a white powder, 275 mg (40%). IR data (in CHzClz): 2112,2062,2019 (qco)), 1614 (V(COO)~~,,J, 1350 ( Y ( C ~ )cm-'. ~ ) lH NMR (CDCl3): 6 2.52 (2H, d, CHH(anti)),4.06 (2H, d, CHH (syn)), 5.18 (lH, m, CH), 7.19-7.30 (3H, m, phenyl), 7.76-7.80 (2H, m, phenyl). 13C NMR (CDC13): 6 60.9 ( C H z ) , 108.2 (CH), 127.7, 129.4, 130.8, 133.7 (phenyl), 170.7 (PhCOO), 189.8 and 192.1 (M - CO). Complex 2c was obtained by a procedure similar to that for l a from the reaction of (q3-2-methallyl)Ru(C0)3Br(357 mg, 1.12 mmol) with silver acetate (189 mg, 1.13mmol), as white needles, 55 mg (16%). mp: 52-55 "C. Anal. Calcd for CgH1005Ru: C, 36.12; H, 3.37. Found: C, 35.61; H, 3.24. IR data (in n-pentane): 2109, 2060,2008 (v(coJ, 1638 (v(COO)aaym) cm-l. 'H NMR (CDC13): 6 1.80 (3H, s, cH&Oo), 2.03 (3H, s, CH3 (2-methallyl), 2.30 (2H, s, CHH (anti)), 3.85 (2H, s, CHH (SF)). 13C NMR (CDCla): 6 22.62 (CH&Oo), 26.54 (CH3(2methallyl)), 60.72 (CHz), 128.25 ((CH~)ZC(CH~)), 175.65 (CHSCOO),190.06 and 193.65 (M - CO). Similarly, complex 2d was synthesized from (q3-C3Hs)Ru(CO)z(PPhdBr (332 mg, 0.598 mmol) and silver acetate (154 mg, 0.598 mmol), as white microneedle crystals, 20 mg (6%). mp: 37-39 "C. Anal. Calcd for C Z ~ H Z ~ O ~ PC,R 57.80; U: H, 4.46. Found: C, 57.51; H, 4.51. lH NMR (CDCl3): 6 1.22 (3H, s, C&), 2.02 (lH, m, CHz(anti)), 2.38 (lH, d, J = 13.35 Hz, CH, (anti)),3.61 ( l H , d, J = 7.91 Hz, CHz (syn)), 3.88 (lH, m, CHZ(syn)), 5.15 (lH, m, CHI, 7.30-7.49 (15H, m, 3 C a s ) . 13C NMR (CDC13): 6 22.98 (CH3),56.45, 56.76 (CHz), 62.77 (CHz), 106.06 (CHI, 128.29-133.88 (phenyl, CHI, 175.13 (CHsCOO), 197.2 and 198.4 (M - CO). Preparation of [(tlS-C~H~)Ru(CO)sl+(OTD(2e). Treatment of complex l a (501 mg, 1.64 mmol) with silver acetate in CHzClz (30 mL) at room temperature (422 mg, 1.64 "01) for 15 h under an argon atmosphere in the dark affords a
colorless solution and a yellow precipitate. The colorless solution was chromatographed on neutral A 1 2 0 3 (2 cm i.d. x 2 cm; eluent CHZClz), and solvent was removed under vacuum. The resulting white powder was washed with n-pentane and dried under vacuum. Recrystallization was performed from CHCl3-n-pentane; yield 290 mg (47%). mp: 84-85 "C. Anal. Calcd for C ~ H ~ F ~ O ~ SC,R22.41; U : H, 1.34; F, 15.19. Found: C, 22.67; H, 1.43; F, 15.37. IR data (in CHZC12): 2128, 2078, 2037 ( Y C C O ) )cm-'. 'H NMR (CDC13): 6 2.64 (2H, d, J = 13.36 Hz, CHH (anti)),4.35 (2H, d, J = 7.42 Hz, CHH (syn)), 5.37 (lH, m, CH). 13CNMR (CDCl3): 6 60.33 (CHz), 109.07 (CH), 118.64 (CF3, q, J = 318 Hz), 187.23 and 190.13 (M - CO). Preparation of Cp*RuC12(qS-CH2CHCHPh) (3a). A mixture of Cp*RuCl(COD) (509 mg, 1.34 mmol), cinnamyl chloride (0.373 mL, 2.68 mmol), and THF (20 mL) was placed in a two-necked 50-mL Pyrex flask equipped with a magnetic stirring bar under an argon atmosphere, and the mixture was stirred a t room temperature for 15 h. The color of the solution changed from orange t o deep red gradually, the solvent was evaporated, and the residue was washed with two portions of n-pentane (2 mL). The supernatant was removed, and the crude crystal was dried under vacuum and recrystallized from the CHZClz-Et20 by cooling at -78 "C to give 3a in 69% yield (393 mg; red-brown powder). mp: 192-193 "C dec. IR data (KBr): 758, 695 cm-l. lH NMR (CDC13): 6 1.55 (15H, s, 5 CpCHd, 2.50 (lH, d, J = 9.3 Hz, CHH (anti)), 4.09 (lH, d, J = 10.7 Hz, CHPh) 4.11 (lH, d, J = 6.4 Hz, CHH (syn)), 5.54 (lH, ddd, J = 6.4, 9.3, 10.7 Hz, CHzCH), 7.26-7.30 (5H, m, Ph). 13C NMR (CDCl3): 6 9.7 (CpCH31, 62.9 ( C H z ) , 90.4 (CHPh), 92.8 (CHCHz), 104.0 ( C p ) , 127.8, 129.3, 131.3, and 135.4 (phenyl C3, C4, C2, Cl). X-ray Structure Determination of [(qs-C~&)Ru(CO)~(H20)lf(OTf)- (2f). Crystal data, data collection, and refineare summent parameters of [(q3-C3Hs)Ru(C0)3(HzO)~+(OMmarized in Table 1. A single crystal of [(q3-C3H5)Ru(C0)3(HzO)I+(OTf- was mounted and placed on a Rigaku AFC-7R difiactometer. The unit cell was determined by the automatic indexing of 25 centered reflections and confirmed by examination of the axial photographs. Intensity data were collected using graphite-monochromated Mo Ka X-radiation (, =I0.710 69 A). Check reflections were measured every 100 reflections, and the data were scaled accordingly and corrected for Lorentz, polarization, and absorption effects. The structure was solved using Patterson and standard difference map techniques on a IRIS computer using SAF'191.39 Systematic absences were consistent uniquely with the space group P1 (No. 2). Bond
Nucleophilic and Electrophilic Allylation Reactions
Organometallics, Vol. 14,No. 4,1995 1953
Table 7. Atomic Coordinates and BiJB, for 2f atom 1
X
Y
z
Be,
0.34655(4) 0.2371(1) -0.0083(5) 0.2265(6) 0.0851(6) 0.6175(5) 0.6296(5) 0.2470(5) 0.109 1( 5 ) 0.3749(5) 0.2919(5) 0.1526(4) 0.5123(6) 0.5241(6) 0.2873(6) 0.3262(6) 0.2669(6) 0.1382(6) 0.1320(7) 0.4342 0.2430 0.3494 0.1119 0.0442 0.2004 0.0834
0.24869(3) -0.2660(1) -0.3964(5) -0.3380(5) -0.1951(5) 0.0965(4) 0.5003(3) 0.1561(4) -0.2377(4) -0.1549(3) -0.3816(3) 0.3604(3) 0.15 12(4) 0.4089(4) 0.1922(4) 0.2780(5) 0.1448(5) 0.0990(5) -0.2991(7) 0.3057 0.3287 0.0854 0.0061 0.1400 0.4520 0.3399
0.15664(4) 0.2 19l(2) 0.3455(6) 0.5116(5) 0.4625(5) 0.1686(5) 0.1842(5) -0.2284(4) 0.1017(5) 0.2903(6) 0.1731(6) 0.1423(4) 0.1649(6) 0.1693(6) -0.0884(6) 0.4303(6) 0.3660(6) 0.2262(7) 0.3970(8) 0.5207 0.4252 0.3999 0.1618 0.1963 0.1576 0.0341
3.175(7) 4.30(3) 10.5(1) 11.0(1) 11.1(2) 6.24(10) 5.96(9) 5.89(9) 6.9(1) 7.4(1) 7.2(1) 4.61(7) 4.3(1) 4.2(1) 4.1(1) 4.7(1) 4.8(1) 5.0(1) 6.6(2) 6(1) 4.5(9) 5.9(10) 5.7(10) 3.3(8) 9.4(10) 11.3(8)
Table 8. Atomic Coordinates and BJB,, for 3a atom
X
Y
Z
Be,
0.20907(5) 0.2608(2) 0.1820(2) 0.2619(8) 0.3 17(1) 0.3282(9) 0.3823(8) 0.4262(8) 0.4821(9) 0.4898(9) 0.4472(9) 0.3916( 10) 0.1 194(7) 0.0832(7) 0.1016(8) 0.1494(8) 0.1623(8) 0.1 14(1) 0.0295(7) 0.069( 1) 0.1699(8) 0.202( 1)
0.31955(6) 0.4772(2) 0.4354(3) 0.229( 1) 0.279(2) 0.244(1) 0.283 1) 0.382( 1) 0.413( 1) 0.358(2) 0.263(2) 0.226( 1) 0.333( 1) 0.3346(9) 0.239( 1) 0.173(1) 0.235( 1) 0.415(1) 0.423( 1) 0.205( 1) 0.0591(9) 0.202(2)
0.2653 0.1468(5) 0.4898(5) 0.458(2) 0.368(2) 0.207(2) 0.084(2) 0.120(2) 0.005(2) -0.138(3) -0.170(2) -0.054(2) 0.062(2) 0.219(2) 0.297(2) 0.193(2) 0.049(2) -0.065(2) 0.275(4) 0.463(2) 0.2 16(2) -0.099(2)
2.77(1) 4.20(8) 5.8(1) 4.9(4) 4.7(4) 333) 4.7(4) 5.4(4) 6.1(5) 6.6(5) 6.9(5) 5.7(5) 4.3(3) 3.8(3) 5.8(5) 3.6(3) 3.4(3) 7.2(5) 7.0(4) 7.1(5) 4.7(4) 7.4(5)
Reaction of la, 2a, and 2e with NaCH(C0fle)Z. In a typical procedure, THF solution of NaCH(C0OMe)z (-0.6 mM), which was prepared from dimethyl malonate and NaH in oil, was added to the THF solution (1.0 mL) of the complexes (la, 2a, 2e) (0.10 mmol) at room temperature under an argon atmosphere, and the mixture was stirred for 24-40 h. The resulting yellow solution containing yellow powder was analyzed by GLC and GC-MS. Reaction of 3a with Nucleophiles. A mixture of C ~ * R U C ~ ~ ( ~ ~ ~ - C H(3a; ~ C0.20 H Cmmol), H ) 1,5-cyclooctadiene (0.24 mmol), and CDzClz (0.50 mL) was placed in an NMR measurement tube (5mm id.) under an argon atmosphere and dissolved completely. Then, piperidine (0.40 mmol) was added. The reaction was carried out at room temperature and observed by IH NMR. Yield of the product was determined by IH NMR based on the phenyl proton. In the case of carbonucleophile, employing 3 equiv of acetylacetone (0.60 mmol) and N-methylpiperidine (0.24 mmol), the reaction was performed similarly. 1-(1-Phenyl-2-propeny1)piperidine (4). Colorless liquid. Kugelrohr distillation (bp 65 "C, 0.5 mmHg) from the reaction illustrated in Scheme 4. Anal. Calcd for C I ~ H I ~ N C,: 83.53; H, 9.51; N, 6.96. Found: C, 83.23; H, 9.51; N, 6.94, for a 93:7 mixture of 4 and 5. MS: mlz 201 (M+). IR data (neat): 1638, 994, 918, 756, 700 cm-'. 'H NMR (CDC13): 6 1.28-1.36 (2H, m, CHz), 1.43-1.54 (4H, m, CHz), 2.16-2.24 (2H, m, CHzN), 2.32-2.36 (2H, m, CHzN), 3.56 (lH, d, J = 8.8 Hz, NCHPh), 4.99 ( l H , dd, J = 1.7, 10.0 Hz, (E)-CH2=), 5.09 ( l H , ddd, J = 1.0, 1.7, 17.1 Hz, (Z)-CH2=), 5.87 (lH, ddd, J =8.6, 10.0, 17.1 Hz, CH-), 7.08-7.30 (5H, m, Ph). 13C NMR (CDC13): 6 24.6 (CH2),26.0 (CH2),52.4 (CHzN), 75.4 (NCHPh), 115.8 (=CH2), 140.3 (CH=), 126.8, 127.9, 128.3, 142.3 (phenyl C-4, (2-2, C-3,
c-1).
(E)-l-(3-Phenyl-2-propenyl)piperidine (5). Colorless liquid. Kugelrohr distillation (bp 75 "C, 0.5 mmHg) from the reaction illustrated in Scheme 4. MS, mlz 201 (M+). IR data (neat): 1653, 965, 739, 693 cm-'. 'H NMR (CDCL): 6 1.441.46 (2H, m, CHz), 1.56-1.64 (4H, m, CHZ), 2.43 (4H, br, CHzN), 3.11 (2H, d, J = 6 . 4 H z , CH2CH=), 6.30 (lH, d t , ' J = 15.6 Hz, 3J= 6.8 Hz, CH=CHPh), 6.49 (lH, d, J = 15.6 Hz, =CHPh), 7.18-7.38 (5H, m, Ph). 13C NMR (CDC13) 6 24.3 (CHz), 26.0 (CHz), 54.6 (CHzN), 61.9 (CHzCH-), 127.2 (CH=CHPh), 132.5 (=CHPh), 126.2, 127.3, 128.5, 137.0 (phenyl (2-2, c-4, (2-3, (2-1). 3-Acetyl-4-phenyl-5-hexen-2-one (6). White solid. Kugelrohr distillation (bp 95 "C, 0.5 mmHg). mp: 35.0-36.0 "C. Anal. Calcd for C14H1602: C, 77.74; H, 7.46. Found: C, 77.66; H, 7.35. MS: mlz 216 (M+). IR data (KBr): 1738-1696,1640, 992,930,754,702 cm-l. IH NMR (CDCl3): 6 1.86 (3H, s, CH31, 2.23 (3H, S, CH3), 4.17 (lH, dd, J =7.3, 11.5 Hz, O h ) , 4.28 lengths and angles for [(173-C3H5)R~(C0)3(H~O)l+(OTf)are (lH, d, J = 11.5 Hz, CHCHPh), 5.04 (lH, d, J = 10.3 Hz, (E)given in Tables 2 and 3. Atomic coordinates and BisJBeqare CH2=), 5.06 (lH, d, J = 17.1 Hz, (Z)-CHz=), 5.86 (lH, ddd, J given in Table 7. = 7.3, 10.3, 17.1 Hz, CH=), 7.08-7.30 (5H, m, Ph). 13CNMR (CDC13): 6 29.3 (CH3), 29.8 ( C H 3 ) , 49.5 (CHCHPh), 73.8 X-ray Structure Determination of Cp*RuClz($(CHCHPh), 116.2 (=CHz), 137.9 (CH=), 126.9, 127.7, 128.6, CH&HCHPh) (3a). Crystal data, data collection, and refine139.6 (Phenyl C-4, C-2, C-3, (2-11, 202.3 (C=O), 202.4 (C=O). ment parameters are summarized in Table 1, and general procedure is as described for [(rl3-C3H5)Ru(C0)3(H~O)I+(OTf)(using SHEIX8642 1. Systematic absences were consistent Acknowledgment. We are very grateful to Profesuniquely with the space group Pna21 (No. 33). Bond lengths sor Shigeyoshi Sakaki of Kumamoto University for his and angles are listed in Tables 4 and 5. Atomic coordinates helpful discussion and MO calculation. This work was and Bi,,JBes are given in Table 8. partly supported by a Grant-in-Aid for Scientific ReReaction of la, 2a, and 2e with Aldehydes. In a typical search from the Japanese Ministry of Education, Science procedure, a mixture of the complex 2a (9.8 mg, 0.034 mmol), and Culture. Portions of this work have been reported benzaldehyde (29 mg, 0.27 mmol), and Et3N (78 mg, 0.77 previously: Kondo, T.; Ono, H.; Mitsudo, T.; Watanabe, mmol) in CHC4 was stirred at room temperature for 48-72 h Y. Abstracts of Papers, The 63th Annual Meeting of under an argon atmosphere. The resulting orange-brown Chemical Society of Japan; Osaka, Japan, March 1992. solution was analyzed by GLC and GC-MS. ~________
(41)Hai-Fu, F.Structure Analysis Programs with Intelligent Control; Rigaku Corp.: Tokyo, 1991. (42) Sheldrick, G. M. In Crystallographic Computing 3; Sheldrick, G. M., Kruger, C., Goddard, R., Eds.; Oxford University Press: New York, 1985; p 175.
Supplementary Material Available: Lists of complete crystallographic data of 2f and 3a (30 pages). Ordering information is given on any current masthead page. OM9408369
