Asymmetric synthesis of aryl/vinyl alkyl carbinol esters via Ni-catalyzed reductive arylation/vinylation of 1-chloro-1-alkanol esters

• Published in: Chemical science (Cambridge) Vol. 13; no. 28; pp. 8365 - 8370
• Main Authors: Sun, Deli, Tao, Xianghua, Ma, Guobin, Wang, Jifen, Chen, Yunrong
• Format: Journal Article
• Language: English
• Published: CAMBRIDGE Royal Soc Chemistry 20.07.2022; Royal Society of Chemistry; The Royal Society of Chemistry
• Subjects: Aromatic compounds; Asymmetry; Carbonyls; Chemistry; Chemistry, Multidisciplinary; Esters; Functional groups; Hydroxyl groups; Physical Sciences; Science & Technology; Substrates; HYDROGENATION; REAGENTS; ENANTIOMERICALLY PURE ALCOHOLS; ALLYLIC ALCOHOLS; AMINES; KINETIC RESOLUTION; ALDEHYDES; DERACEMISATION
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/D2SC02806A

We report herein an asymmetric Ni-catalyzed cross-electrophile coupling approach to prepare enantioenriched aryl/vinyl alkyl carbinol esters through arylation/vinylation of easily accessible racemic 1-chloro-1-alkanol esters with aryl/vinyl electrophiles. The method features a broad substrate scope as demonstrated by more than 60 examples including the challenging chiral allylic esters. It tolerates a wide array of functional groups including alkenyl, carbonyl and free hydroxyl groups that may not survive in conventional carbonyl reduction and addition methods. The synthetic utility of the present work was showcased by facile preparation of a few key intermediates and the modification of chiral drugs and naturally occurring compounds. Finally, we describe an efficient one-pot procedure for this method.