Double stereodifferentiation in the Lewis acid promoted C-glycosidation of activated glycals with chiral (E)-crotylsilanes

✍ Scribed by James S. Panek; Jennifer V. Schaus

• Publisher: Elsevier Science
• Year: 1997
• Tongue: French
• Weight: 653 KB
• Volume: 53
• Category: Article
• ISSN: 0040-4020
• DOI: 10.1016/s0040-4020(97)00358-x

✦ Synopsis

Lewis acid promoted C-glycosidation reactions of activated glycals with chiral (E)-crotylsilanes were found to be highly regio-and diastereoselective. The reactions of chiral silane reagents proceed with the formation of a new C-C bond at C6 of the pyran ring with concomitant migration of C5-C6 double bond to the C5-C4 position of the pyran ring. The reactions are highly diastereoface selective as the crotylsilane (carbon nucleophile) approaches the derived oxonium ion anti to the C2 substituent. The stereochemical relationship between the methyl bearing stereogenic center at the C 1' position and the C6 position of the pyran is defined by the chirality of the silane reagent as the configuration of the C-Si bond determines the stereochemistry of the C l'-methyl group. Our experiments have shown that the pair wise combination of the glycals with the chiral silane reagents give high levels of selectivity resulting from the existence of strong stereocbemical control elements within each reaction component. The topological bias is principally controlled by stereoelectronic effects of the pyran oxonium ion and by the facial bias of the silane reagent. Levels of diastereoselectivity ranged from 10 to 30 : 1 (ot/[~ ratio) in the presence of BF3-OEt 2 which was found to be with TMSOTf the most effective Lewis acids to promote the reactions. Consistent with the behavior of these silane reagents and an anti-SE" mechanism, of the four possible diastereomers only the two isomers derived from the C I' stereoehemical relationship are detectable.