Seeman Jeffrey I
Department of Chemistry, University of Richmond, Richmond, VA 23173, USA.
Chem Rec. 2023 Jan;23(1):e202200239. doi: 10.1002/tcr.202200239. Epub 2023 Jan 11.
Previous publications in this series on the history of the development of the Woodward-Hoffmann rules revealed why Woodward and Hoffmann were prime candidates to solve the pericyclic no-mechanism problem. This publication explains why it was the collaborative team of R. B. Woodward and Roald Hoffmann who did solve this mechanistic problem in a series of five communications in the Journal of the American Chemical Society in 1965. That is, the reasons why Woodward and Hoffmann were the perfect team, and why their individual capabilities, experiences, and qualities provided the perfect synergy are described. In part, this was the right time and the right place for them both, but the synergies were fundamental, intrinsic and idiosyncratic as a collaborative pair. Their orbital symmetry rules provided the mechanism of all concerted pericyclic reactions including electrocyclizations, cycloadditions, and sigmatropic rearrangements. Why it was 1965 and not earlier is also discussed.
本系列之前关于伍德沃德-霍夫曼规则发展历程的出版物揭示了为何伍德沃德和霍夫曼是解决周环反应无机理问题的主要人选。本出版物解释了为何正是R. B. 伍德沃德和罗尔德·霍夫曼的合作团队于1965年在美国化学会志上发表的一系列五篇通讯文章中解决了这一机理问题。也就是说，阐述了伍德沃德和霍夫曼成为完美团队的原因，以及他们个人的能力、经验和特质如何实现了完美协同效应。部分原因在于，对他们两人而言这是恰逢其时、地利，但作为一个合作对子，这种协同效应是根本性的、内在的且独具特色的。他们的轨道对称性规则为包括电环化反应、环加成反应和σ迁移重排反应在内的所有协同周环反应提供了反应机理。本文还讨论了为何是在1965年而非更早的时间解决了该问题。
