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Catalytic Construction and Reconstruction of Guanidines:  Ti-Mediated Guanylation of Amines and Transamination of Guanidines

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posted on 12.06.2003, 00:00 authored by Tiow-Gan Ong, Glenn P. A. Yap, Darrin S. Richeson
Bis(guanidinate) titanium imido complexes [{(Me2N)C(NiPr)2}2TiNAr‘] (Ar‘ = 2,6-Me2C6H3 (1a); C6F5 (1b)) are competent catalysts for the guanylation of a variety of arylamines with carbodiimide. The reversible [2 + 2] addition of iPrNCNiPr to 1b is demonstrated and is proposed to be part of the catalytic cycle. Compounds 1a and 1b are also effective precatalysts for the transamination of trialkylguanidines with arylamines to yield aryldialkylguanidines.

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