Issue 41, 2021

Selective propargylic C(sp3)–H activation of methyl-substituted alkynes versus [2 + 2] cycloaddition at a titanium imido template

Abstract

The reaction of the titanium imido complex 1b with 2-butyne leads to the formation of the titanium azadiene complex 2a at ambient temperature instead of yielding the archetypical [2 + 2] cycloaddition product (titanaazacyclobutene) which is usually obtained by combining titanium imido complexes and internal alkynes. The formation of 2a is presumably caused by an initial propargylic C(sp3)–H activation step and quantum chemical calculations suggest that the outcome of this unexpected reactivity is thermodynamically favored. The previously reported titanaazacyclobutene I (which is obtained by reacting 1b with 1-phenyl-1-propyne) undergoes a rearrangement reaction at elevated temperature to give the corresponding five-membered titanium azadiene complex 2b.

Graphical abstract: Selective propargylic C(sp3)–H activation of methyl-substituted alkynes versus [2 + 2] cycloaddition at a titanium imido template

Supplementary files

Article information

Article type
Edge Article
Submitted
08 aug 2021
Accepted
27 sep 2021
First published
28 sep 2021
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2021,12, 13711-13718

Selective propargylic C(sp3)–H activation of methyl-substituted alkynes versus [2 + 2] cycloaddition at a titanium imido template

M. Fischer, M. Manßen, M. Schmidtmann, T. Klüner and R. Beckhaus, Chem. Sci., 2021, 12, 13711 DOI: 10.1039/D1SC04334J

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