Selective Monoacylation of Diols and Asymmetric Desymmetrization of Dialkyl meso-Tartrates Using 2-Pyridyl Esters as Acylating Agents and Metal Carboxylates as Catalysts

Yuki Hashimoto; Chiaki Michimuko; Koki Yamaguchi; Makoto Nakajima; Masaharu Sugiura

doi:10.1021/acs.joc.9b00827

Selective Monoacylation of Diols and Asymmetric Desymmetrization of Dialkyl meso-Tartrates Using 2-Pyridyl Esters as Acylating Agents and Metal Carboxylates as Catalysts

J Org Chem. 2019 Jul 19;84(14):9313-9321. doi: 10.1021/acs.joc.9b00827. Epub 2019 Jun 27.

Authors

Yuki Hashimoto^{1

2}, Chiaki Michimuko², Koki Yamaguchi¹, Makoto Nakajima², Masaharu Sugiura¹

Affiliations

¹ Faculty of Pharmaceutical Sciences , Sojo University , 4-22-1 Ikeda , Nishi-ku, Kumamoto 860-0082 , Japan.
² Graduate School of Pharmaceutical Sciences , Kumamoto University , 5-1 Oe-honmachi , Chuo-ku, Kumamoto 862-0973 , Japan.

PMID: 31199140
DOI: 10.1021/acs.joc.9b00827

Abstract

With 2-pyridyl benzoates as acylating agents and Zn(OAc)₂ as a catalyst, 1,2-diols, 1,3-diols, and catechol were selectively monoacylated. Furthermore, the highly enantioselective desymmetrization of meso-tartrates was achieved for the first time, utilizing 2-pyridyl esters and NiBr₂/AgOPiv/Ph-BOX in CH₃CN or CuCl₂/AgOPiv/Ph-BOX in EtOAc catalyst systems (up to 96% ee). The latter catalyst system was also effective for the kinetic resolution of dibenzyl dl-tartrate.

Publication types

Research Support, Non-U.S. Gov't