Open AccessCarbodiimide Synthesis via Ti-Catalyzed Nitrene Transfer from Diazenes to Isocyanides
Author(s) -
Evan P. Beaumier,
Meghan E. McGreal,
Adam Pancoast,
R. Hunter Wilson,
James T. Moore,
Brendan J. Graziano,
Jason D. Goodpaster,
Ian A. Tonks
Publication year - 2019
Publication title -
acs catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 4.898
H-Index - 198
ISSN - 2155-5435
DOI - 10.1021/acscatal.9b04107
Subject(s) - chemistry , carbodiimide , nitrene , catalysis , ligand (biochemistry) , combinatorial chemistry , isocyanide , redox , alkyl , photochemistry , aryl , yield (engineering) , organic chemistry , materials science , biochemistry , receptor , metallurgy
Simple Ti imido halide complexes such as [Br 2 Ti(N t Bu)py 2 ] 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 Ti II intermediates and provides further evidence that substrate and product "redox noninnocence" can promote unusual Ti redox catalytic transformations.