Abstract
This account describes the development of Ti-catalyzed intermolecular hydroamination reactions of alkynes, achieved in the author’s laboratories during the last five years. Starting from initial ideas and early results with Cp2TiMe2 as a catalyst precursor, mechanistic studies and applications of Cp2TiMe2-catalyzed hydroaminations of alkynes for the synthesis of biologically interesting classes of compounds are presented. Particular attention is paid to the identification of improved second generation catalysts such as Cp*2TiMe2 and Ind2TiMe2.

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