Rhodium-Catalyzed Asymmetric 1,4-Addition of Organoboronic Acids and Their Derivatives to Electron Deficient Olefins

Tamio Hayashi

doi:10.1055/s-2001-14657

Synlett 2001; 2001(Special Issue): 0879-0887
DOI: 10.1055/s-2001-14657

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Rhodium-Catalyzed Asymmetric 1,4-Addition of Organoboronic Acids and Their Derivatives to Electron Deficient Olefins

Tamio Hayashi^*

^*Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502, Japan; Fax + 81-75-753-3988; E-mail: thayashi@kuchem.kyoto-u.ac.jp

Abstract

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Asymmetric 1,4-arylation and -alkenylation was achieved by use of organoboronic acids or their derivatives in the presence of a rhodium catalyst coordined with binap ligand. The reaction conditions are unique in that it is usually carried out in an aqueous solvent at 100 °C. The scope of this asymmetric addition is very broad, α,β-unsaturated ketones, esters, 1-alkenylphosphonates, and 1-nitroalkenes being efficiently converted into the corresponding optically active 1,4-addition products with over 95% enantioselectivity. The catalytic cycle is proposed to involve the enantioselective addition of aryl- or alkenyl-rhodium intermediate to carbon-carbon double bond of the electron deficient olefins as a key step.

asymmetric catalysis - asymmetric 1,4-addition - rhodium complex - organoboronic acids - electron deficient olefins

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