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The Configurational Stability of an Enantioenriched α ‐Thiobenzyllithium Derivative and the Stereochemical Course of Its Electrophilic Substitution Reactions; Synthesis of Enantiomerically Pure, Tertiary Benzylic Thiols [1,2]
Author(s) -
Stratmann Oliver,
Kaiser Bernd,
Fröhlich Roland,
Meyer Oliver,
Hoppe Dieter
Publication year - 2001
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20010119)7:2<423::aid-chem423>3.0.co;2-y
Subject(s) - enantiopure drug , chemistry , electrophile , deprotonation , thiocarbamate , electrophilic substitution , substitution reaction , stereochemistry , derivative (finance) , enantioselective synthesis , medicinal chemistry , organic chemistry , ion , financial economics , economics , catalysis
The lithium compound ( S )‐ 7 , formed by deprotonation of the ( S )‐ S ‐1‐phenylethyl thiocarbamate ( S )‐ 10 , is configurationally stable at −70 °C. Even at elevated temperatures it racemizes only very slowly. It represents the first essentially enantiopure α ‐thiocarbanion derivative and can be utilized in asymmetric synthesis. Most electrophiles (except proton acids) add to ( S )‐ 7 with complete stereoinversion. Cleavage of the substitution products leads to practically enantiopure, tertiary 1‐phenylalkanethiols.