Premium
The Synthesis and Configurational Stability of Enantioenriched α‐Thioallyllithium Compounds and the Stereochemical Course of Their Electrophilic Substitution
Author(s) -
Marr Felix,
Fröhlich Roland,
Wibbeling Birgit,
Diedrich Christian,
Hoppe Dieter
Publication year - 2002
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 - 10.1002/1099-0690(200209)2002:17<2970::aid-ejoc2970>3.0.co;2-j
Subject(s) - chemistry , deprotonation , electrophile , electrophilic substitution , enantioselective synthesis , stereochemistry , lithium (medication) , thio , combinatorial chemistry , organic chemistry , catalysis , medicine , ion , endocrinology
Deprotonation of enantioenriched S ‐allyl N ‐monoalkylmonothiocarbamates furnished the corresponding chiral lithium compounds. The α‐thioallyllithium compounds 9 and 25 were found to be configurationally stable in THF solutions at −78 °C. These represent the first configurationally stable α‐thio‐substituted allyllithium compounds, and they can be utilized in asymmetric synthesis. Alkylations proceeded with stereoinversion or in an anti ‐S E ′ process, while addition to carbonyl compounds took place in a syn ‐S E ′ process. Hydroxyalkylation products were employed as starting material for Ni 0 ‐catalyzed cross‐coupling reactions.