期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 60, 期 24, 页码 13476-13483出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202103327
关键词
cross-coupling; esters; ketones; nickel; Suzuki– Miyaura reactions
资金
- BASF
- National Science and Engineering Research Council of Canada (NSERC)
- Canada Research Chair program
- National Natural Science Foundation of China [21702182, 21873081]
- Fundamental Research Funds for the Central Universities [2020XZZX002-02]
- State Key Laboratory of Clean Energy Utilization [ZJU-CEU2020007]
A new method has been developed to convert alkyl esters into alkyl ketones, resulting in the synthesis of 65 different alkyl ketones with various functional groups and heterocyclic structures. The study found that catalyst-controlled chemoselectivity could activate the C(acyl)-O bond in the substrate, while density functional theory calculations supported the mechanism of the nickel catalytic cycle.
The direct conversion of alkyl esters to ketones has been hindered by the sluggish reactivity of the starting materials and the susceptibility of the product towards subsequent nucleophilic attack. We have now achieved a cross-coupling approach to this transformation using nickel, a bulky N-heterocyclic carbene ligand, and alkyl organoboron coupling partners. 65 alkyl ketones bearing diverse functional groups and heterocyclic scaffolds have been synthesized with this method. Catalyst-controlled chemoselectivity is observed for C(acyl)-O bond activation of multi-functional substrates bearing other bonds prone to cleavage by Ni, including aryl ether, aryl fluoride, and N-Ph amide functional groups. Density functional theory calculations provide mechanistic support for a Ni-0/Ni-II catalytic cycle and demonstrate how stabilizing non-covalent interactions between the bulky catalyst and substrate are critical for the reaction's success.
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