A Base-Mediated Rearrangement of the Benzylic 1,5-Hexadipyridynyl Moiety.

IF 3 4区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY
Wouter A Remmerswaal, Thai-Tony Nguyen, Han Zijan, Fedor Krasovski Slobodian, Ruisheng Xiong, Vadim Kessler, Zhijian Xu, Weiliang Zhu, Mate Erdelyi
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引用次数: 0

Abstract

We report a previously unrecognized base-mediated rearrangement of a benzylic 1,5-hexadipyridynyl moiety. Upon exposure to base, we show this structural motif to rearrange into a constrained vinyl-pyridine substituted cyclobutene. Computational modeling indicates that the rearrangement takes place following a route involving stepwise deprotonation, shifted reprotonation, and 4-π-electrocyclization. Furthermore, non-base-mediates rearrangements, through well-known Cope-like [3,3]-sigmatropic shifts, were found to be high in energy and therefore take a backseat to the base-mediated pathway. This rearrangement may provide a novel reactivity pathway of conjugated systems for synthetic methodology development.

苯基1,5-己二吡啶基部分的碱基介导重排。
我们报告了先前未被识别的碱基介导的苯基1,5-己二吡啶基部分的重排。暴露于碱后,我们显示这个结构基序重新排列成一个受限的乙烯基吡啶取代环丁烯。计算模型表明,重排的过程包括逐步去质子化、移位重排和4 π电环化。此外,非碱基介导的重排,通过众所周知的类coplike[3,3]-信号位移,被发现具有高能量,因此在碱基介导的途径中处于次要地位。这种重排可能为合成方法的发展提供一种新的共轭体系反应性途径。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
ChemPlusChem
ChemPlusChem CHEMISTRY, MULTIDISCIPLINARY-
CiteScore
5.90
自引率
0.00%
发文量
200
审稿时长
1 months
期刊介绍: ChemPlusChem is a peer-reviewed, general chemistry journal that brings readers the very best in multidisciplinary research centering on chemistry. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies. Fully comprehensive in its scope, ChemPlusChem publishes articles covering new results from at least two different aspects (subfields) of chemistry or one of chemistry and one of another scientific discipline (one chemistry topic plus another one, hence the title ChemPlusChem). All suitable submissions undergo balanced peer review by experts in the field to ensure the highest quality, originality, relevance, significance, and validity.
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