Imine complexes insertion into metal-carbon bonds

The insertions of imines into late transition metal-carbon bonds are even less common. In one case, the insertion of an imine into Ni- and Pd-acyl bonds occurs with 2,1-regiochemistry to form an aminoalkyl product (Equation 9.80). Tlus reaction is likely to occur through a polar transition state formed by attack of a nucleophilic nitrogen at the electrophilic acyl carbon. One set of examples of 1,2-insertions of imines into late metal-carbon bonds have been reported. This example involves insertion of N-aryl aldimines into rhodium-aryl complexes containing a labile pyridine ligand (Equation 9.81). The rates of these reactions were inverse order in added pyridine, suggesting that the reaction occurs by an intramolecular migratory insertion mechanism after replacement of the coordinated pyridine by the imine. 

Isocyanide has been widely utilized as a key reagent in organic synthesis. Besides, the insertion of isocyanides into M-C bonds is one of the powerful means for carbon chain construction [16-34]. Insertion of isocyanide into M-C bonds afforded / -iminoacyl-metal intermediates, such as / -iminoacyl-Zr complexes [19-27], which can be conveniently converted to one-carbon elongated products such as imines, aldehydes, or nitriles via various chemical bond cleavage including Zr-C, C=N, and N-R bonds (Scheme 2.8) [29-32]. / -Iminoacyl-Zr complexes... 

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