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Synthesis of Thiol Esters Using PhSZnBr as Sulfenylating Agent: A DFT‐Guided Optimization of Reaction Conditions
Author(s) -
Sancineto Luca,
Tidei Caterina,
Bagnoli Luana,
Marini Francesca,
Lippolis Vito,
Arca Massimiliano,
Lenardão Eder João,
Santi Claudio
Publication year - 2016
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.201600366
Subject(s) - chemistry , reagent , thiol , reactivity (psychology) , solvent , chloride , coordination complex , combinatorial chemistry , functional group , molecule , mechanochemistry , organic chemistry , metal , medicine , alternative medicine , pathology , polymer
The use of PhSZnBr as sulfenylating agent in a solvent‐free protocol to prepare thiol esters in excellent yields from acyl chlorides is reported. The products were efficiently obtained by grinding the neat reagents for 5 min in a mortar. DFT calculations showed that the coordination of solvent molecules to the metal center of PhSZnBr results in the destabilization of the frontier MOs, thus reducing the reactivity towards the acyl chloride compared with solvent‐free conditions. A possible mechanism based on the coordination of the carbonyl group of the acyl chloride to the metal center of PhSZnBr is proposed.