Citation: Xinzhi Li, Xiangwei Ren, Hongli Wu, Wentao Zhao, Xiangyang Tang, Genping Huang. Mechanism and selectivity of copper-catalyzed borocyanation of 1-aryl-1,3-butadienes: A computational study[J]. Chinese Chemical Letters, ;2021, 32(1): 9-12. doi: 10.1016/j.cclet.2020.11.045 shu

Mechanism and selectivity of copper-catalyzed borocyanation of 1-aryl-1,3-butadienes: A computational study

Department of Chem istry, School of Science and Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Tianjin University, Tianjin 300072, China

txy@tju.edu.cn

gphuang@tju.edu.cn

Received Date: 12 October 2020
Revised Date: 19 November 2020
Accepted Date: 19 November 2020
Available Online: 1 December 2020

Figures(6)

Density functional theory calculations have been performed to investigate the copper-catalyzed borocyanation of 1-aryl-1,3-butadienes. The computations show that the regio- and enantioselectivity is determined by the borocupration step. The π-electron withdrawing aryl group at the C¹ atom makes the C⁴ atom more electrophilic than the other carbon atoms, which together with the steric repulsion around the forming C—B bond, results in the experimentally observed exclusive 4,3-regioselectivity. The origins of the enantioselectivity were attributed to the steric effect and π-π stacking interaction between the butadiene moiety and the ligand.
- Copper catalyst,
- Borocyanation,
- Mechanism,
- Selectivity,
- DFT calculations
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