Diastereoselectivity in the boron aldol reaction of -alkoxy and ,-bis-alkoxy methyl ketones

Autor(es)

Fernandes, Alessandra A. G. ^[1] ; Leonarczyk, Ives A. ^[2] ; Ferreira, Marco A. B. ^[2] ; Dias, Luiz Carlos ^[1]

Afiliação do(s) autor(es)

^[1] Univ Estadual Campinas, Inst Chem, BR-13083970 Campinas, SP - Brazil

^[2] Fed Univ Sao, Dept Chem, Ctr Excellence Res Sustainable Chem CERSusChem, BR-13565905 Carlos - Brazil

• Tipo de documento: Artigo Científico
• Fonte: ORGANIC & BIOMOLECULAR CHEMISTRY; v. 17, n. 12, p. 3167-3180, MAR 28 2019.
• Citações Web of Science: 1

Resumo

In this work, using DFT calculations, we investigated the 1,4 and 1,5 asymmetric induction in boron enolate aldol reactions of -alkoxy and ,-bisalkoxy methyl ketones. We evaluated the steric influence of alkyl substituents at the position and the stereoelectronic influence of the oxygen protecting groups at the and positions. Theoretical calculations revealed the origins of the 1,4 asymmetric induction in terms of the nature of the -substituent. The synergistic effect between the ,-syn and ,-anti-bisalkoxy stereocenters was elucidated. In the presence of the -alkoxy center, the reaction proceeds through the Goodman-Paton 1,5-stereoinduction model, experiencing a minor influence of the -alkoxy center. (AU)

• Processo FAPESP: 15/08541-6 - Ressonância magnética nuclear: além da determinação estrutural
• Beneficiário: Claudio Francisco Tormena
• Modalidade de apoio: Auxílio à Pesquisa - Temático
• Processo FAPESP: 14/50249-8 - Green chemistry: sustainable synthetic methods employing benign solvents, safer reagents, and bio-renewable feedstock
• Beneficiário: Arlene Gonçalves Corrêa
• Modalidade de apoio: Auxílio à Pesquisa - Programa Centros de Pesquisa em Engenharia