Rearrangement Reactions of Tritylcarbenes: Surprising Ring Expansion and Computational Investigation

Chemistry : a European Journal
Klaus BanertJoachim Friedrich

Abstract

As a rule, acetylides and sulfonyl azides do not undergo electrophilic azide transfer because 1,2,3-triazoles are usually formed. We show now that treatment of tritylethyne with butyllithium followed by exposure to 2,4,6-triisopropylbenzenesulfonyl azide leads to products that are easily explained through the generation of short-lived tritylethynyl azide and its secondary product cyanotritylcarbene. Furthermore, it is demonstrated that tritylcarbenes generally do not produce triphenylethenes exclusively, as was stated in the literature. Instead, these carbenes always yielded also (diphenylmethylidene)cycloheptatrienes (heptafulvenes) as side products. This result is supported by static DFT, coupled cluster, and ab initio molecular dynamics calculations. From these investigations, the fused bicyclobutane intermediate was found to be essential for heptafulvene formation. Although the bicyclobutane is also capable of rearranging to the triphenylethene product, only the heptafulvene pathway is reasonable from the energetics. The ethene is formed straight from cyanotritylcarbene.

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Citations

Dec 4, 2015·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Klaus BanertXiaoqing Zeng
Sep 24, 2020·Organic Letters·Ming-Yang XiaoJun-An Ma
Aug 26, 2017·The Journal of Organic Chemistry·Mohammed H Al-HunitiMitchell P Croatt

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