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The synthesis of α‐aminosilanes by a highly enantio‐ and regioselective copper‐catalyzed hydroamination of vinylsilanes is reported. The system employs Cu‐DTBM‐SEGPHOS as the catalyst, diethoxymethylsilane as the stoichiometric reductant, and O‐benzoylhydroxylamines as the electrophilic nitrogen source. This hydroamination reaction is compatible with differentially substituted vinylsilanes, thus providing...
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