Transition-Metal-Catalyzed Synthesis of α-Chiral Allylsilanes.

[103] The key to obtain quaternary -chiral allylsilanes with perfect -regioselectivity and excellent enantiomeric purity was to perform the reaction in the presence of 6 mol% of chiral SPSiOL--derived bisphosphite ligand B 91 b with 5 mol% of NiBr SB 2 sb --DME and 20 mol% of LiO I t i -Bu. [63] Thus, when the reaction was carried out with as little as 0.125 mol% of PdCl( SP 3 sp -C SB 3 sb H SB 5 sb )] SB 2 sb in the presence of 0.5 mol% of ligand B 74 b , 1,4-hydrosilylated cyclopentadiene was obtained with excellent enantiomeric purity. Keywords: allylsilanes; allylic substitution; conjugate addition; enantio-selectivity; hydrosilylation; regioselectivity EN allylsilanes allylic substitution conjugate addition enantio-selectivity hydrosilylation regioselectivity 2609 2638 30 08/17/23 20230901 NES 230901 Graph 1 Introduction The small electronegativity difference between carbon and silicon results in low polarization of the C-Si bond which makes it a relatively robust covalent bond, providing organosilicon compounds with high bench stability and easy handling. The reaction with ( I E i )-vinylaluminum reagents was performed in the presence of as little as 1 mol% of CuCl SB 2 sb -2H SB 2 sb O and 0.5 mol% of complex B 56 b . [Extracted from the article]