e.g. Filippa Pettersson or Cancer Res. 75(6) , 1102-12, (2015) or 10.1002/anie.201600521
Tetrahedron
Nucleophilic substitutions at silicon: Evidence for ion-pair dissociation as controlling factor of the stereochemistry and a simple mechanistic proposal
RJP Corriu, C Guerin
Index: Corriu, R. J. P.; Guerin, C. Tetrahedron, 1981 , vol. 37, # 14 p. 2467 - 2472
Stereochemical and kinetic data are reported for reactions between organolithiums or LiAlH4 and some chiral organosilanes. They rule out a mechanism involving complexation control, such as the SNi-Si process proposed by Sommer et al. Electrophilic assistance to the cleavage of a Si-X bond does not control the stereochemistry, but acts as an additional factor which can facilitate the inversion by increasing the ability of the leaving group to ...