Controlled selectivity through reversible inhibition of the catalyst: Stereodivergent semihydrogenation of alkynes

Abstract

Catalytic semihydrogenation of internal alkynes using H2 is an attractive atom-economical route to various alkenes, and its stereocontrol has received widespread attention, both in homogeneous and heterogeneous catalysis. Herein, a novel strategy is introduced, whereby a poisoning catalytic thiol is employed as a reversible inhibitor of a ruthenium catalyst, resulting in the first controllable H2-based semihydrogenation of internal alkynes. Both (E)- and (Z)-alkenes were obtained efficiently and highly-selectively, under very mild conditions, using a single homogenous acridine-based ruthenium catalyst. Mechanistic studies indicate that the (Z)-alkene is the reaction intermediate leading to the (E)-alkene, and that addition of a catalytic amount of bidentate thiol impedes the Z-E isomerization step by forming stable ruthenium thiol(ate) complexes, while still allowing the main hydrogenation reaction to proceed. Thus, the absence or presence of catalytic thiol controls the stereoselectivity of this alkyne semihydrogenation, affording either the (E)-isomer as the final product, or halting the reaction at the (Z)-intermediate. The developed system, which is also applied to the controllable isomerization of a terminal alkene, demonstrates how selective metal catalysis can be achieved by reversible inhibition of the catalyst with a simple auxiliary additive.