Carbodiimide Synthesis via Ti-Catalyzed Nitrene Transfer from Diazenes to Isocyanides.

ACS Catalysis
Evan P BeaumierIan A Tonks

Abstract

Simple Ti imido halide complexes such as [Br2Ti(N t Bu)py2]2 are competent catalysts for the synthesis of unsymmetrical carbodiimides via Ti-catalyzed nitrene transfer from diazenes or azides to isocyanides. Both alkyl and aryl isocyanides are compatible with the reaction conditions, although product inhibition with sterically unencumbered substrates sometimes limits the yield when diazenes are employed as the oxidant. The reaction mechanism has been investigated both experimentally and computationally, wherein a key feature is that the product release is triggered by electron transfer from an η 2-carbodiimide to a Ti-bound azobenzene. This ligand-to-ligand redox buffering obviates the need for high-energy formally TiII intermediates and provides further evidence that substrate and product "redox noninnocence" can promote unusual Ti redox catalytic transformations.

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Citations

Mar 2, 2021·Chemical Communications : Chem Comm·Jongho SoYunho Lee
Aug 28, 2020·Chemical Society Reviews·Manfred Manßen, Laurel L Schafer
Jun 15, 2021·Chemical Science·Evan P BeaumierIan A Tonks
Dec 2, 2020·Inorganic Chemistry·Anders ReinholdtDaniel J Mindiola
Apr 3, 2020·Journal of the American Chemical Society·Evan P BeaumierIan A Tonks
Aug 24, 2021·Accounts of Chemical Research·Ian A Tonks

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