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Decomposition of 2‐Mercaptoethyl O ‐Ester: S N 2 Displacement or Acyl Transfer? A Theoretical Study
Author(s) -
Zhang Shenshen,
Qi Chenze,
Wang Chen
Publication year - 2014
Publication title -
chinese journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.28
H-Index - 41
eISSN - 1614-7065
pISSN - 1001-604X
DOI - 10.1002/cjoc.201300874
Subject(s) - chemistry , moiety , thiol , decomposition , acyl group , alcohol , medicinal chemistry , displacement (psychology) , alkyl , atom (system on chip) , stereochemistry , organic chemistry , psychology , psychotherapist , computer science , embedded system
Abstract The mechanism for the decomposition of 2‐mercaptoethyl O ‐ester was theoretically investigated. The mechanism that 2‐mercaptoethyl O ‐ester undergoes an S N 2 displacement of the O atom by the S atom on α ‐C is much favored over the mechanism of N‐to‐S acyl transfer. The length of the alcohol moiety has large effects on the decomposition efficiency of thiol‐substituted alkyl O ‐esters. The reactivities of these esters are controlled by distortion energies. Only 2‐mercaptoethyl O ‐ester can undergo the decomposition at room temperature due to the low distortion energy to achieve the transition state geometry. If the thiol group of 2‐mercaptoethyl O ‐ester is replaced by an amino group, the N‐to‐N acyl transfer mechanism is more favored than the S N 2 displacement mechanism.