Dimeric Manganese-Catalyzed Hydroalkenylation of Alkynes with a Versatile Silicon-Based Directing Group

Herein, we present a manganese-catalyzed, branched-selective hydroalkenylation of terminal alkynes, under mild conditions through facile installation of a versatile silanol as a removable directing group. With an alkenyl boronic acid as the coupling partner, this reaction produces stereodefined (E,E)-1,3-dienes with high regio-, chemo- and stereoselectivity. The protocol features mild reaction conditions such as room temperature and an air atmosphere, while maintaining excellent functional group compatibility. The resulting 1,3-dienesilanol products serve as versatile building blocks, as the removal of the silanol group allows for the synthesis of both branched terminal 1,3-dienes for downstream coupling reactions, as well as stereoselective construction of linear (E,E)-1,3-dienes and (E,E,E)- or (E,E,Z)-1,3,5-trienes. In addition, a Diels-Alder cycloaddition can smoothly and selectively deliver silicon-containing pentasubstituted cyclohexene derivatives. Mechanistic investigations, in conjunction with DFT calculations, suggest a bimetallic synergistic activation model to account for the observed enhanced catalytic efficiency and good regioselectivity.

Automated summary

Here we describe a manganese-catalyzed hydroalkenylation reaction that selectively introduces branched groups to terminal alkynes under mild conditions using a removable silanol directing group. Coupling with an alkenyl boronic acid partner yields (E,E)-1,3-dienes with high regio-, chemo- and stereoselectivity. The reaction proceeds at room temperature in air and is compatible with various functional groups. The resulting 1,3-dienesilanol products can be used as versatile building blocks for downstream synthesis of branched or linear 1,3-dienes and 1,3,5-trienes by removing the silanol group. Additionally, a Diels-Alder cycloaddition delivers silicon-containing pentasubstituted cyclohexenes. Mechanistic studies and DFT calculations support a bimetallic synergistic activation model for the enhanced catalytic efficiency and regioselectivity observed.