Planar Dinuclear Copper-Based Hydrogen-Bonded Organic Framework with Synergy Catalysis for High-Performance Hydroboration of Alkynes

Abstract Dinuclear metal synergistic catalysis (DMSC) has been well established as an effective strategy for enhancing catalytic efficiency in various fields. However, the design of catalysts for the DMSC-enabled hydroboration of terminal alkynes has been rarely reported. Herein, we report the synthesis of a novel copper-based hydrogen-bonded organic framework (HOF), denoted as Cu-PzDC. Benefiting from its planar dinuclear Cu units, Cu-PzDC exhibits exceptionally high catalytic efficiency toward the hydroboration of terminal alkynes, achieving complete conversion within merely 30 min at room temperature without the need of inert atmosphere. This catalytic system affords the synthetically valuable β-(E)-vinylboronates with 99% selectivity and demonstrates a broad substrate compatibility covering 29 examples. DFT calculations reveal the synergistic effect between two adjacent Cu sites, which enables the simultaneous activation of boryl species and phenylacetylene and brings them into close proximity.