On the Preparation and Determination of Configurational Stability of Chiral Thio-and Bromo [D1] methyllithiums

A Wieczorek, F Hammerschmidt

Index: Wieczorek, Anna; Hammerschmidt, Friedrich Journal of Organic Chemistry, 2012 , vol. 77, # 22 p. 10021 - 10034

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Citation Number: 8

Abstract

Thio-and bromo [D1] methyllithiums (ee 99%) were generated from the respective stannanes by tin–lithium exchange at temperatures ranging from 0 to− 95° C. Thio [D1] methyllithiums 6 were found to be microscopically configurationally labile on the time scale of the thiophosphate-α-mercaptophosphonate rearrangement even at− 95° C. Thio [D1] methyllithiums 13a and 13b underwent a thia-[2, 3]-Wittig rearrangement down to− 95° C ...