通过脱硫二锂化实现噻吩的芳构化转变

Aromatic Metamorphosis of Thiophenes by Means of Desulfurative Dilithiation.

作者信息

Kaga Atsushi, Iida Hirokazu, Tsuchiya Shun, Saito Hayate, Nakano Koji, Yorimitsu Hideki

机构信息

Department of Chemistry, Graduate School of Science, Sakyo-ku, Kyoto, 606-8502, Japan.

Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, 2-24-16 Naka-cho, Koganei, Tokyo, 184-8588, Japan.

出版信息

Chemistry. 2021 Mar 8;27(14):4567-4572. doi: 10.1002/chem.202005223. Epub 2021 Feb 5.

DOI:10.1002/chem.202005223

PMID:33349986

Abstract

A new mode of aromatic metamorphosis has been developed, which allows thiophenes and their benzo-fused derivatives to be converted to a variety of exotic heteroles. This transformation involves 1) the efficient generation of key 1,4-dianions by means of desulfurative dilithiation with lithium powder and 2) the subsequent trapping of the dianions with heteroatom electrophiles in a one-pot manner. Via the desulfurative dilithiation, the sulfur atoms of thiophenes are replaced also with a carbon-carbon double bond or a 1,2-phenylene for the construction of benzene rings.

摘要

一种新的芳香族变态模式已经被开发出来，它能使噻吩及其苯并稠合衍生物转化为各种奇特的杂环化合物。这种转化涉及：1）通过用锂粉进行脱硫双锂化高效生成关键的1,4 - 二阴离子；2）随后用杂原子亲电试剂以一锅法捕获二阴离子。通过脱硫双锂化，噻吩的硫原子也被碳 - 碳双键或1,2 - 亚苯基取代以构建苯环。