Homoallyl alcohols allylzincation

The mechanism of the Zn chloride-assisted, palladium-catalyzed reaction of allyl acetate (456) with carbonyl compounds (457) has been proposed [434]. The reaction involves electroreduction of a Pd(II) complex to a Pd(0) complex, oxidative addition of the allyl acetate to the Pd(0) complex, and Zn(II)/Pd(II) transmetallation leading to an allylzinc reagent, which would react with (457) to give homoallyl alcohols (458) and (459) (Scheme 157). Substituted -lactones are electrosynthesized by the Reformatsky reaction of ketones and ethyl a-bromobutyrate, using a sacrificial Zn anode in 35 92% yield [542]. The effect of cathode materials involving Zn, C, Pt, Ni, and so on, has been investigated for the electrochemical allylation of acetone [543]. 

Failure for Grignard reagents to undergo similar additions to homoallylic amines may be explained by the greater stability of the complexes between an amine and zinc rather than magnesium. By contrast, addition of allylzinc bromide to allyl or homoallyl alcohols proceeded considerably less efficiently compared to amines and the regioselectivity was reversed (equation 55)81. 

Several methods promoted by a stoichiometric amount of chiral Lewis acid 38 [51] or chiral Lewis bases 39 [52, 53] and 40 [53] have been developed for enantioselective indium-mediated allylation of aldehydes and ketones by the Loh group. A combination of a chiral trimethylsilyl ether derived from norpseu-doephedrine and allyltrimethylsilane is also convenient for synthesis of enan-tiopure homoallylic alcohols from ketones [54,55]. Asymmetric carbonyl addition by chirally modified allylic metal reagents, to which chiral auxiliaries are covalently bonded, is also an efficient method to obtain enantiomerically enriched homoallylic alcohols and various excellent chiral allylating agents have been developed for example, (lS,2S)-pseudoephedrine- and (lF,2F)-cyclohex-ane-1,2-diamine-derived allylsilanes [56], polymer-supported chiral allylboron reagents [57], and a bisoxazoline-modified chiral allylzinc reagent [58]. An al-lyl transfer reaction from a chiral crotyl donor opened a way to highly enantioselective and a-selective crotylation of aldehydes [59-62]. Enzymatic routes to enantioselective allylation of carbonyl compounds have still not appeared. 

Allylzinc and allylchromium reagents coordinated by chiral ligands have variable degrees of success in the preparation of optically active homoallylic alcohols. 

HMPA, through which a carbonylative coupling of aUyl and alkyl groups proceeds to provide unsymmetrical ketone and Pd(0) species. On the other hand, in the absence of HMPA, an alkyl-allyl exchange reaction takes place between I and organozinc and gives rise to the mixture of symmetrically substituted dialkylpalladium HI and allylzinc. Car-bonylation of the intermediate HI produces symmetrical ketone and regenerates Pd(0). Allylzinc thus formed is responsible for the formation of the lactones and the homoallyl alcohol in Scheme 26. ... 

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