Premium
Borane‐Catalyzed Cross‐Metathesis Strategy for Facile Transformation of Cyclic (Alkyl)(Amino)Germylenes
Author(s) -
Rao Bin,
Wang Liliang,
Kinjo Rei
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201811574
Subject(s) - borane , chemistry , catalysis , metathesis , alkyl , silane , isomerization , silanes , medicinal chemistry , salt metathesis reaction , silylation , stereochemistry , organic chemistry , polymerization , polymer
A borane B(C 6 F 5 ) 3 ‐catalyzed metathesis reaction between the Si−C bond in the cyclic (alkyl)(amino)germylene (CAAGe) 1 and the Si−H bond in a silane (R 3 SiH; 2 ) is reported. Mechanistic studies propose that the initial step of the reaction involves Si−H bond activation to furnish an ionic species [ 1 ‐SiR 3 ] + [HB(C 6 F 5 ) 3 ] − , from which [Me 3 Si] + [HB(C 6 F 5 ) 3 ] − and an azagermole intermediate are generated. The former yields Me 3 SiH concomitant with the regeneration of B(C 6 F 5 ) 3 whereas the latter undergoes isomerization to afford CAAGes bearing various silyl groups on the carbon atom next to the germylene center. This strategy allows the straightforward synthesis of eight new CAAGes starting from 1 .