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Title: Lewis base-catalyzed reactions of SiX 3-based reagents with C=O, C=N (n → σ*)
Authors: Malkov, Andrei V.
Kocovsky, Pavel
Issue Date: 2016
Publisher: Wiley
Citation: MALKOV, A.V. and KOCOVSKY, P., 2016. Lewis base-catalyzed reactions of SiX 3-based reagents with C=O, C=N (n → σ*). IN: Vedejs, E. and Denmark, S.E. (eds.) Lewis Base Catalysis in Organic Synthesis, Weinheim, Germany: Wiley, pp. 1011-1038.
Abstract: Nucleophilic addition to carbonyl and heterocarbonyl compounds is the cornerstone of organic synthesis, highlighted by the classical examples of Grignard reactions, aldol condensation, and H4 reductions. However, when less reactive nucleophiles are employed, such as allyl-silane, activation is required. This chapter focuses on the activation of silicon reagents by chiral Lewis bases. The field of nucleophilic activation of the reagents 3/4 was pioneered by Sakurai and coworkers, who, in the late 1980s, reported on a highly diastereoselective allylation of aldehydes with allyltriha-losilanes 3 and 4 in the presence of stoichiometric amounts of CsF. If two molecules of the Lewis base are involved in the formation of the catalytically active species, or if a biden-tate catalyst is used, the reaction would proceed through the cationic hexacoordinate transition complex. The early phosphoramides exhibited modest enantioselectivity in the allylation reaction but played an important role in the mechanistic elucidation and development of the second generation of catalysts.
Description: This book chapter is in closed access.
Version: Accepted for publication
DOI: 10.1002/9783527675142.ch20
URI: https://dspace.lboro.ac.uk/2134/22507
Publisher Link: http://dx.doi.org/10.1002/9783527675142.ch20
ISBN: 9783527675142
Appears in Collections:Closed Access (Chemistry)

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