ChemInform Abstract: Asymmetric Catalysis with Silicon‐Based Cuprates: Enantio‐ and Regioselective Allylic Substitution of Linear Precursors.

Preparations of Silyl Anions

“…154,167 The in situ generated silylcopper can be utilized in several reactions, such as the enantioselective silylation of α,β-unsaturated phosphine oxide derivative, 168 enantioselective synthesis of α-chiral propargylic silanes, 169 hydrosilylation of benzonornadiene derivatives, 170 silylation of benzylic ammonium triflates, 171 stereoselective addition to strained alkenes, 172 synthesis of 1,1-disilylated alkanes from geminal dibromides, 173 and in numerous other applications. 157 164 , 174 175 176 177 178 179 180 181 182 183 184 185 186 187 188 189 190…”

“…The protocol involves the activation of the Si–B bond and transmetalation through σ bond metathesis (Scheme 60 ). 161 , 163 164 165 166 This approach to silylcopper synthesis is preferable to its preparation from extremely reactive silyllithium, which is a concern in the presence of sensitive functional groups, and is a good alternative to stoichiometric copper-based silyl anions. 154,167 The in situ generated silylcopper can be utilized in several reactions, such as the enantioselective silylation of α,β-unsaturated phosphine oxide derivative, 168 enantioselective synthesis of α-chiral propargylic silanes, 169 hydrosilylation of benzonornadiene derivatives, 170 silylation of benzylic ammonium triflates, 171 stereoselective addition to strained alkenes, 172 synthesis of 1,1-disilylated alkanes from geminal dibromides, 173 and in numerous other applications.…”