The first Csp3-Csp2 cross-coupling using aldehydes as latent α-alkoxyalkyl anion equivalents has been achieved. The synergistic palladium/copper-catalyzed reaction of aromatic aldehydes and aryl bromides with a silylboronate afforded the three-component coupling products, silyl-protected benzhydrol derivatives. The reaction pathway involves the catalytic formation of a nucleophilic α-silyloxybenzylcopper(i) species followed by its palladium-catalyzed cross-coupling with aryl bromides.
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http://dx.doi.org/10.1039/c8cc01055b | DOI Listing |
Angew Chem Int Ed Engl
May 2024
State Key Laboratory and Institute of Elemento-Organic Chemistry College of Chemistry,Frontiers Science Center for New Organic Matter, Nankai University, Tianjin, 300071, China.
The construction of two distal stereocenters through a single catalytic process is of great interest in organic synthesis. While there are some successful reports regarding stereodivergent preparation of 1,3- or 1,4-stereocenters, the more challenged 1,5-nonadjacent stereocenters have never been achieved in a stereodivergent fashion. Herein we describe a synergistic palladium/copper catalysis for 1,4-difunctionalization reactions of 1,3-dienes, providing access to 1,5-nonadjacent quaternary stereocenters.
View Article and Find Full Text PDFBeilstein J Org Chem
February 2020
Division of Pharmaceutical Sciences, Graduate School of Medical Sciences, Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan.
The allylic cross-coupling using aromatic aldehydes as α-alkoxyalkyl anions is described. The synergistic palladium/copper-catalyzed reaction of aromatic aldehydes, allylic carbonates, and a silylboronate produces the corresponding homoallylic alcohol derivatives. This process involves the catalytic formation of a nucleophilic α-silyloxybenzylcopper(I) species and the subsequent palladium-catalyzed allylic substitution.
View Article and Find Full Text PDFChem Commun (Camb)
June 2018
Division of Pharmaceutical Sciences, Graduate School of Medical Sciences, Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan.
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