Abstract

AbstractThe intermolecular anti‐Markovnikov hydroamination of vinylsilanes was achieved utilizing five silyl‐substituted ortho‐terphenoxide yttrium complexes. The highest activity was observed for the most sterically encumbered triphenylsilyl‐substituted complex. Excellent activity and complete anti‐Markonikov selectivity were obtained for a variety of benzylic and aliphatic primary and secondary amines. Interestingly, the reaction with 2‐picolylamine produced the hydroaminoalkylation product rather than the hydroamination product. Reaction of dimethyldivinylsilane resulted in a range of 1,4‐azasilinanes via sequential hydroamination/endocyclization in good yields.

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