Реферат: In asymmetric cross-coupling and hydrosilylation reactions, as well as in asymmetric hydrogenation, under the action of chiral bis(diphenyl-phosphine) metal complexes having C2 symmetry axis of the chelate ring, simple stereochemical rules define the relationship between the prevailing configuration of the product and the bis(diphenylphosphine) complex conformation. In the cross-coupling reactions of Grignard reagents with alkenyls or aryls, in which nickel complexes participate as catalysts, the rules of the λ-(R), δ-(S) type [1] are valid, and the prevailing product configuration is determined by the complex conformation, the order of substituent priorities and the reaction type. In asymmetric hydrosilylation of acetophenone or substituted imines with diphenylsilane under the action of rhodium complexes, the δ-, chair-δ-(R); λ, chair-λ-(S) relationships exist. For each of the above reactions, the chiral complexes of the same conformational series (the λ, chair-λ, boat-λ or the δ, chair-δ, boat-δ) catalyze formation of products with the same prevailing configuration, (R) or (S), which is characteristic of the given reaction and metal. In acetophenone hydrosilylation with diphenylsilane in the presence of rhodium complexes with chiral phosphinite-aminophosphine, phosphiniteamine and phosphine-amine ligands based on amino acids, the ((R)-(R), (S)-(S)) relationship between the product configuration and the ligand configuration is observed.

Библиографическая ссылка: Pavlov V.A. , Zhorov E.Y. , Voloboev A.A. , Klabunovskii E.I.
Relationship between product configuration and complex conformation in asymmetric catalysis on metal complexes (cross-coupling and hydrosilylation reactions)
Journal of Molecular Catalysis. 1990. V.59. N1. P.119-135. DOI: 10.1016/0304-5102(90)85092-v OpenAlex

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W1994836147

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OpenAlex	10

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