Iron- and bismuth-catalyzed asymmetric Mukaiyama aldol reactions in aqueous media

Authors: Kitanosono, Taku; Ollevier, Thierry; Kobayashi, Shu
Abstract: We have developed asymmetric Mukaiyama aldol reactions of silicon enolates with aldehydes catalyzed by chiral Fe II and Bi III complexes. Although previous reactions often required relatively harsh conditions, such as strictly anhydrous conditions, very low temperatures (-78 C), etc., the reactions reported herein proceeded in the presence of water at 0 C. To find appropriate chiral water-compatible Lewis acids for the Mukaiyama aldol reaction, many Lewis acids were screened in combination with chiral bipyridine L1, which had previously been found to be a suitable chiral ligand in aqueous media. Three types of chiral catalysts that consisted of a Fe II or Bi III metal salt, a chiral ligand (L1), and an additive have been discovered and a wide variety of substrates (silicon enolates and aldehydes) reacted to afford the desired aldol products in high yields with high diastereo- and enantioselectivities through an appro- priate selection of one of the three catalytic systems. Mechanistic studies elucidated the coordination environments around the Fe II and Bi III centers and the effect of additives on the chiral catalysis. Notably, both Brønsted acids and bases worked as efficient additives in the Fe II-catalyzed reactions. The assumed catalytic cycle and transition states indicated important roles of water in these efficient asymmetric Mukaiyama aldol reactions in aqueous media with the broadly applicable and versatile catalytic systems.
Document Type: Article de recherche
Issue Date: 2 October 2013
Open Access Date: 16 March 2016
Document version: AM
This document was published in: Chemistry - an Asian journal, Vol. 8 (12), 3051-3062 (2013)
Alternative version: 10.1002/asia.201301149
Collection:Articles publiés dans des revues avec comité de lecture

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