Copper-Catalyzed Enantioselective Borylative Allyl-Allyl Coupling of Allenes and Allylic -Dichlorides

Overview

Journal ACS Catal

Publisher American Chemical Society

Date 2023 May 1

PMID 37123595

Authors

Martin Pineiro-Suarez

Andres M Alvarez-Constantino

Martin Fananas-Mastral

Affiliations

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Abstract

A catalytic asymmetric reaction between allenes, bis(pinacolato)diboron, and allylic -dichlorides is reported. The method involves the coupling of a catalytically generated allyl copper species with the allylic -dichloride and provides chiral internal 1,5-dienes featuring ()-configured alkenyl boronate and alkenyl chloride units with high levels of chemo-, regio-, enantio-, and diastereoselectivity. The synthetic utility of the products is demonstrated with the synthesis of a range of optically active compounds. DFT calculations reveal key noncovalent substrate-ligand interactions that account for the enantioselectivity outcome and the diastereoselective formation of the ()-alkenyl chloride.

Citing Articles

Switching Selectivity in Borylative Allyl-Allyl Cross-Coupling through Synergistic Catalysis.

Vazquez-Galinanes N, Sciortino G, Pineiro-Suarez M, Toth B, Maseras F, Fananas-Mastral M J Am Chem Soc. 2024; 146(31):21977-21988.

PMID: 39046799 PMC: 11311230. DOI: 10.1021/jacs.4c07188.

Copper-catalyzed asymmetric allylic substitution of racemic/ substrates.

Li J, Huang J, Wang Y, Liu Y, Zhu Y, You H Chem Sci. 2024; 15(22):8280-8294.

PMID: 38846404 PMC: 11151816. DOI: 10.1039/d4sc02135e.

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