带有手性2-恶唑烷酮辅助基团的香豆素衍生物的新型不对称光二聚反应。

Novel asymmetric photodimerization reaction of coumarin derivatives bearing a chiral 2-oxazolidinone auxiliary.

作者信息

Itoh Kennosuke, Odate Fumiya, Karikomi Takuma, Obe Keishi, Miyamori Tsutomu, Kamiya Hideaki, Yoza Kenji, Nagai Kenichiro, Fujii Hideaki, Suga Hiroyuki, Tokunaga Ken

机构信息

Laboratory of Medicinal Chemistry, School of Pharmacy, Kitasato University 5-9-1 Shirokane, Minato-ku Tokyo 108-8641 Japan

Medicinal Research Laboratories, School of Pharmacy, Kitasato University 5-9-1 Shirokane, Minato-ku Tokyo 108-8641 Japan.

出版信息

RSC Adv. 2019 Apr 23;9(22):12365-12369. doi: 10.1039/c9ra00822e. eCollection 2019 Apr 17.

DOI:10.1039/c9ra00822e

PMID:35515875

原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9063662/

Abstract

A novel asymmetric photodimerization reaction of coumarin derivatives bearing the ()-4-benzyl-2-oxazolidinone auxiliary provides only the -head-to-tail (-HT) dimer with moderate diastereoselectivity (up to 75 : 25). The mechanism of complete -HT selectivity and moderate diastereoselectivity is proposed based on the result of density functional theory (DFT) calculation. The benzyl group of the ()-4-benzyl-2-oxazolidinone auxiliary in combination with a Lewis acid exerts effective diastereofacial shielding of the reaction site.

摘要

带有（）-4-苄基-2-恶唑烷酮辅助基团的香豆素衍生物的一种新型不对称光二聚反应仅提供具有中等非对映选择性（高达75∶25）的头对头（-HT）二聚体。基于密度泛函理论（DFT）计算结果，提出了完全-HT选择性和中等非对映选择性的机理。（）-4-苄基-2-恶唑烷酮辅助基团的苄基与路易斯酸结合对反应位点产生有效的非对映面屏蔽作用。