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DFT Study of Brønsted Acid Catalyzed Nitroso Aldol Reaction Between Achiral Enamines and Nitrosobenzene: The Reason for Regio‐ and Enantioselectivity
Author(s) -
Akakura Matsujiro,
Kawasaki Masanori,
Yamamoto Hisashi
Publication year - 2008
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200800369
Subject(s) - nitrosobenzene , chemistry , nitroso , regioselectivity , aldol reaction , catalysis , brønsted–lowry acid–base theory , hydrogen bond , organic chemistry , organocatalysis , nitroso compounds , enantioselective synthesis , medicinal chemistry , molecule
Abstract The regio‐ and enantioselectivity of the nitroso aldol reaction between achiral enamines and nitrosobenzene catalyzed by chiral Brønsted acid catalysts (TADDOL or 1‐naphthylglycolic acid) were investigated in experimental and theoretical studies. The use of a model involving a simple organic acid (MeOH or AcOH) revealed that the reaction was catalyzed by two or more molecules of the organic acid and that the transition‐state structure encompassed several hydrogen bonds. The role of hydrogen bonding in the regioselectivity was also examined carefully. The enantioselectivity in the reaction catalyzed by chiral organic acids ( S , S )‐TADDOL and ( S )‐1‐naphthylglycolic acid was also confirmed through computational study.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)