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Synthesis of Metal Nanoparticles Supported on Carbon Nanotube with Doped Co and N Atoms and its Catalytic Applications in Hydrogen Production
Published on: December 6, 2021
Copper Nanoclusters with Exposed Active Sites for Highly Efficient Protoboration of C-C Multiple Bonds
Shaoke Zhang1,2, Songwei Wen2
1Advanced Institute for Ocean Research, Southern University of Science and Technology (SUSTech), Shenzhen 518055, China.
Abstract:
Although atomically precise metal nanoclusters bridge homogeneous and heterogeneous catalysis, their application in the protoboration of C-C unsaturated bonds remains challenging. Herein, we report a stable copper nanocluster (Cu6-1) featuring exposed active sites, which successfully enables efficient protoboration of alkynes. This catalyst can be readily synthesized on a gram scale and exhibits ultrahigh catalytic efficiency under ambient conditions (room temperature and air atmosphere), achieving a turnover number (TON) of up to 32,000. The reaction demonstrates excellent regio- and stereoselectivity, and the substrate scope has been successfully expanded to alkenes and enynes. More importantly, Cu6-1 overcomes the recyclability issues of traditional catalysts, retaining its activity over eight consecutive cycles with no significant deactivation, thus offering a highly efficient and robust platform for the synthesis of organoboron compounds.
Related Concept Videos
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
Carbocations
Heterogeneous Catalysis
Regioselectivity and Stereochemistry of Hydroboration
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
Hydroboration-Oxidation of Alkenes
Bonding in Metals
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