Asymmetric Palladium Migration for Synthesis of Chiral-at-Cage o-Carboranes.

Autor: Guo C; Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China., Zhang J; Department of Chemistry, The Chinese University of Hong Kong Shatin, N.T., Hong Kong, China., Ge Y; Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China., Qiu Z; Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China.; International Joint Laboratory of Catalytic Chemistry, Innovation Institute of Carbon Neutrality, Department of Chemistry, College of Sciences, Shanghai University, Shanghai, 200444, China., Xie Z; Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China.; Shenzhen Grubbs Institute and Department of Chemistry, Southern University of Science and Technology, Shenzhen, 518055, China.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Oct 22, pp. e202416987. Date of Electronic Publication: 2024 Oct 22.
DOI: 10.1002/anie.202416987
Abstrakt: Metal migration strategy can offer BH functionalization of o-carboranes at different positions from where initial bond activation occurs to achieve bifunctionalized o-carboranes in one reaction. We report in this article an enantioselective 3,4-bifunctionalization of o-carboranes via asymmetric Pd migration with a high efficiency and up to 98 % ee. This asymmetric catalysis has a broad substrates scope, leading to the preparation of a class of chiral-at-cage o-carborane derivatives. The enantiocontrol model is suggested on the basis of density functional theory (DFT) results, where the chiral Trost ligand plays a crucial role in this enantioselective Pd migration from exo-alkenyl sp 2 C to the cage B(4) position of o-carborane.
(© 2024 Wiley-VCH GmbH.)
Databáze: MEDLINE
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