Abstract
Defect-engineered metal–organic frameworks (DEMOFs) are emerging advanced materials. The construction of DEMOFs is of great significance; however, DEMOF-based catalysis remains unexplored. (E)-vinylboronates, an important building block for asymmetric synthesis, can be synthesized via the hydroboration of alkynes. However, the lack of high-performance catalysts considerably hinders their synthesis. Herein, a series of DEHKUST-1 (HKUST = Hong Kong University of Science and Technology) (Da–f) catalysts with missing occupation of linkers at Cu nodes were designed by partially replacing benzene-1,3,5-tricarboxylate (H3BTC) with defective connectors of pyridine-3,5-dicarboxylate (PYDC) to efficiently promote the hydroboration of alkynes. Results showed that the Dd containing 0.8 doping ratio of PYDC exhibited remarkable catalytic activity than the defect-free HKUST-1. This originated from the improved accessibility for reactants towards the Lewis acid active Cu sites of DEHKUST-1 due to the presence of plenty of rooms next to the Cu sites and enhanced coordination ability in such ‘defective’ HKUST-1. Dd had high selectivity (>99 %) and yield (>96 %) for (E)-vinylboronates and extensive functional group compatibility for terminal alkynes. Density functional theory (DFT) calculations were performed to elucidate the mechanism of hydroboration. Compared with that of defect-free HKUST-1, the low energy barrier of DEHKUST-1 can be attributed to the lower coordination number of Cu sites and enhanced accessibility of Cu active sites towards reagents.
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