Stephen R. Wilson, G. Georgiadis, H. Khatri
May 1, 1980
Citations
0
Influential Citations
47
Citations
Journal
Journal of the American Chemical Society
Abstract
The reaction of 1,3-dithiolanes with n-butyllithium results in fragmentation to the corresponding thiocarbonyl compound followed by further reaction with n-butyllithium. All four types of thiocarbonyl reactions are observed: reduction, Saddition, C-addition, double addition. Synthetic applications of this reaction for the synthesis of secondary mercaptans and 1,2-carbonyl transposition (23 -, 24a-c) are described. Umpolung' of carbonyl reactivity via 1,3-dithiane anions such as 1 has had substantial impact on synthetic organic chemistry. In contrast, anion 2 has been r e p ~ r t e d ~ , ~ to undergo facile elimination to form ethylene. This hypothesis was apparently based on the work of Schonberg4 (eq l ) , who showed