Takuo Sone, S. Ozaki, N. C. Kasuga
Jun 1, 1995
Citations
0
Influential Citations
17
Citations
Journal
Bulletin of the Chemical Society of Japan
Abstract
cis-Dimethyl(η1-allyl)(triphenylphosphine)gold(III), cis-[AuMe2(η1-allyl)(PPh3)] (η1-allyl = allyl (1), crotyl (2), methallyl (3)) has been synthesized by reaction of cis-[AuMe2X(PPh3)] (X = I, NO3) with corresponding Grignard reagents. X-Ray structure analysis of 2 shows that 2 has a typical square planar cis configuration and the crotyl ligand binds to Au by η1-mode: orthorhombic, space group P212121, a = 9.816(2), b = 23.208(4), c = 9.5290(9) A, Z = 4, R(Rw) = 0.037(0.041) with use of 2551 reflections. Reactions of 2 with HCl and Br2 selectively give 1-butene and 3-bromo-1-butene, respectively, indicating γ-regioselectivity of the reactions. Compounds 1—3 react with aldehydes and ketones to give the corresponding homoallyl alcohols. C–C bond formation also takes place at the γ-position of η1-allyl moiety selectively. The rate of the allylation reaction of carbonyl compounds decreases in the order of methallyl (3) > allyl (1) > crotyl (2) gold(III) complexes. The homoallyl alcohol formed by the reaction...