Premium
Direct Catalytic Access to N‐Silylated Enamines from Enolizable Imines and Hydrosilanes by Base‐Free Dehydrogenative SiN Coupling
Author(s) -
Hermeke Julia,
Klare Hendrik F. T.,
Oestreich Martin
Publication year - 2014
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/chem.201402866
Subject(s) - deprotonation , electrophile , chemistry , imine , ruthenium , catalytic cycle , catalysis , hydride , silicon , reagent , medicinal chemistry , photochemistry , polymer chemistry , ion , organic chemistry , metal
A procedure for the synthesis of otherwise difficult‐to‐make N‐silylated enamines, that is masked enamines derived from primary amines, is reported. The approach is based on formation of a silyliminium ion and subsequent abstraction of the acidified α‐proton rather than α‐deprotonation of the enolizable imine followed by reaction with an electrophilic silicon reagent. The silicon electrophile, stabilized by a sulfur atom, is generated by cooperative activation of an SiH bond at the RuS bond of a tethered ruthenium(II) thiolate complex. After transfer of the silicon cation onto the imine nitrogen atom, the remaining ruthenium(II) hydride fulfills the role of the base. Deprotonation and release of dihydrogen close the catalytic cycle. The net reaction is a dehydrogenative SiN coupling of enolizable imines and hydrosilanes.