Issue 5, 2013

Fast transimination in organic solvents in the absence of proton and metal catalysts. A key to iminemetathesis catalyzed by primary amines under mild conditions

Abstract

Amineimine exchange reactions of sterically unhindered reactants were found to be surprisingly fast at room temperature in a variety of nonaqueous solvents in the absence of proton and metal catalysts. The reaction mechanism suggested by ab initio calculations in the gas phase involves nucleophilic addition to the C[double bond, length as m-dash]N bond in concert with proton transfer from the amine NH bond to the imine nitrogen via a highly imbalanced transition state. These very fast transimination reactions were utilized in the catalysis of imine metathesis. Imine metathesis, usually carried out in organic solvents at high temperature in the presence of metal catalysts, occurs smoothly at room temperature in the presence of primary amines under nonacidic conditions as a result of coupled transimination processes. Kinetic data fully consistent with the proposed reaction mechanism were obtained.

Graphical abstract: Fast transimination in organic solvents in the absence of proton and metal catalysts. A key to imine metathesis catalyzed by primary amines under mild conditions

Supplementary files

Article information

Article type
Edge Article
Submitted
30 Jan 2013
Accepted
01 Mar 2013
First published
01 Mar 2013

Chem. Sci., 2013,4, 2253-2261

Fast transimination in organic solvents in the absence of proton and metal catalysts. A key to imine metathesis catalyzed by primary amines under mild conditions

M. Ciaccia, R. Cacciapaglia, P. Mencarelli, L. Mandolini and S. Di Stefano, Chem. Sci., 2013, 4, 2253 DOI: 10.1039/C3SC50277E

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