Allyllithium, chiral

With 1,3-Chirality Transfer from Enantiomerically Enriched Allyllithium Derivatives... 

Enantiomerically enriched l-(diisopropylaminocarbonyloxy)allyllithium derivatives (Section 1.3.3.3.1.2.) add to carbonyl compounds with syn-l,3-chirality transfer21, giving good evidence for a pericyclic transition state in the main reaction path (Section 1.3.3.1.). However, since the simple diastereoselectivity and the degree of chirality transfer are low, for synthetic purposes a metal exchange with titanium reagents or trialkyltin halides (Section D.1.3.3.3.8.2.3.) is recommended. 

Scheme 40 Diastereoselective addition of y-substituted allyllithium and allylzinc reagents to a chiral diimine...

For applications of the chiral allyllithium (240) and related reagents to double asymmetric reactions with 2-(f-butyldimethylsilyloxy)propanal T. KrSmer and D. Hoppe, Tetrahedron Lett., 1987, 28, 5149. 

Remarkably, the enantioselective deprotonation with (-)-3 can be extended to various systems. Thus, substituted indenes like 22 can be stereoselectively deprotonated leading to chiral allyllithiums which after reaction with electrophiles furnish chiral 1,3-disubsti-tuted indenes such as 23 with excellent enan-tioselectivity (Eq. 12). [19]... 

Allyltitanium reagents have been used in the homo-aldol reaction [76]. Enan-tiodivergent tuning by virtue of the titanium reagents of chiral l-oxyallyUithium substrates leads to enantiomeric homo-aldol products with excellent enantiomeric excess. Hoppe and coworkers found the first example of a chiral nonracemic allyllithium with configurative stabiHty [77]. In their work they described the lithiation of optically pure aUyl carbamates. These lithiated allylic carbamates are substrates for homo-aldol reactions. The so-derived chiral allyllithium compounds can be transmetaUated to titanium in order to facilitate a subsequent aldol reaction (Scheme 3.48) [76a]. 

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