通过狄尔斯-阿尔德反应合成吡喃萘醌时意外的区域选择性。

Unexpected regioselectivity in the synthesis of pyranonaphthoquinone via the Diels-Alder reaction.

作者信息

Cui Yi, Jiang Hao, Li Zhengtao, Wu Na, Yang Zhen, Quan Junmin

机构信息

Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education and Beijing National Laboratory for Molecular Science (BNLMS), College of Chemistry, Peking University, Beijing 100871, China.

出版信息

Org Lett. 2009 Oct 15;11(20):4628-31. doi: 10.1021/ol901902v.

DOI:10.1021/ol901902v

PMID:19757828

Abstract

The unusual regioselectivity in the Diels-Alder reactions of pyranoquinone 1 with (4,4-dimethoxybuta-1,3-dien-2-yloxy)trimethylsilane 2 are explored by both computations and experiments. The regioselectivity is controlled by the electrostatic interaction of the lactone ring-oxygen and the vicinal quinone oxygen on the transition structure, which can be tuned by the terminal methyl group of the butadienes.

摘要

通过计算和实验探索了吡喃醌1与(4,4 - 二甲氧基丁 - 1,3 - 二烯 - 2 - 基氧基)三甲基硅烷2的狄尔斯 - 阿尔德反应中不寻常的区域选择性。区域选择性由内酯环氧与过渡结构上邻位醌氧的静电相互作用控制，这种相互作用可通过丁二烯的末端甲基进行调节。