Tetrahedron

The effects of C–S and C–Se bonds on torquoselectivity: stereoselective olefination of α-thio and α-selenoketones with ynolates

T Yoshikawa, S Mori, M Shindo

Index: Yoshikawa, Takashi; Mori, Seiji; Shindo, Mitsuru Tetrahedron, 2009 , vol. 65, # 43 p. 8832 - 8838

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Citation Number: 7

Abstract

Highly Z-selective olefination of acyclic α-thio and α-selenoketones with ynolates has been achieved, and the theoretical calculations of the transition states in the ring-opening of the intermediates, the β-lactone enolates, revealed that the torquoselectivity was controlled by the secondary orbital interactions between the σ orbital of the C–S bond or a lone pair orbital on the S and σ∗ orbitals of the breaking C–O bond, and the σ orbital of the breaking C–O ...