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.
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.