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Improvement in the One‐Carbon Chain Extension of Esters with Dimethylsulfoxonium Methylide
Author(s) -
Luong Hoa,
LussLusis Eduard,
Tanoury Gerald J.,
Nugent William A.
Publication year - 2013
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.201300526
Subject(s) - chemistry , oxonium ion , carboxylate , ylide , hydrolysis , ab initio , reagent , carbon chain , computational chemistry , chain (unit) , organic chemistry , stereochemistry , ion , physics , astronomy
A recent report suggests that the reaction of dimethylsulfoxonium methylide with esters does not produce a chain‐extended sulfur ylide as previously reported, but rather affords the corresponding carboxylate salt. We have investigated this assertion by using a combination of ab initio molecular orbital calculations, spiking studies, and isotopic labeling. The formation of carboxylate is unambiguously demonstrated to arise through hydrolysis involving adventitious water, principally derived from moisture in commercial trimethylsulfoxonium chloride. Careful vacuum drying of this reagent diminishes the competing hydrolytic pathway resulting in higher yields for the chain‐extension reaction than previously reported.