Heteroatom??Guided Torquoselective Olefination of α??Oxy and α??Amino Ketones via Ynolates

M Shindo, T Yoshikawa, Y Itou, S Mori…

Index: Shindo, Mitsuru; Yoshikawa, Takashi; Itou, Yasuaki; Mori, Seiji; Nishii, Takeshi; Shishido, Kozo Chemistry - A European Journal, 2006 , vol. 12, # 2 p. 524 - 536

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Citation Number: 39

Abstract

Abstract Ynolates were found to react with α-alkoxy-, α-siloxy-, and α-aryloxyketones at room temperature to afford tetrasubstituted olefins with high Z selectivity. Since the geometrical selectivity was determined in the ring opening of the β-lactone enolate intermediates, the torquoselectivity was controlled by the ethereal oxygen atoms. From experimental and theoretical studies, the high Z selectivity is induced by orbital and steric interactions rather ...