(Z)-Selective Hydrosilylation and Hydroboration of Terminal Alkynes Enabled by Ruthenium Complexes with an N-Heterocyclic Carbene Ligand.

Metal-catalyzed trans-1,2-hydrosilylations and hydroborations of terminal alkynes that generate synthetically valuable (Z)-alkenylsilanes and (Z)-alkenylboranes remain challenging due to the (E)-selective nature of the reactions and the formation of the thermodynamically unfavorable (Z)-isomer. The development of new, efficient catalytic systems for the (Z)-selective hydrosilylation and hydroboration of terminal alkynes is thus highly desirable from a fundamental perspective as it would deepen our understanding of the metal-catalyzed (Z)-selective hydrosilylation and hydroboration of terminal alkynes. This personal account describes our research for developing a ruthenium complex that can efficiently catalyze the hydrosilylation and hydroboration of terminal alkynes, and for exploring the factors controlling (Z)-selectivity of the reactions. Our effort into the activation of B-protected boronic acids, R-B(dan) (dan=naphthalene-1,8-diaminato), that was believed not to participate in Suzuki-Miyaura cross-coupling, is also discussed.