The chemistry of amines, amides and other nitrogen-containing compounds plays a central role in organic synthesis because a great number of natural, pharmaceutical and agrochemical compounds contain a C-N bond.1 N-Alkylation reactions using the hydrogen borrowing process are of interest from the point of view of sustainability, since they replace highly reactive and genotoxic reagents such as alkyl halides or tosylates with less reactive reagents such as alcohols.2The development of more active catalysts is of paramount importance to increase the efficiency of this reaction, improving the catalyst loading and the reaction rate, particularly when the substrates have great steric bulk or require the use of polar solvents.Monomeric Ir(III) complexes containing a modified Cp* have been synthesised and their catalytic activities have been compared with [Cp*IrCl2]2, achieving higher yields and faster hydrogen borrowing reactions than the dimer. More than 20 substrates containing aryl, heteroaryl and alkyl groups were prepared in 62-99% yields; among them, primary and secondary alcohols and primary and secondary amines have been used. Furthermore, a broad range of functional groups were tolerated, such as halides, nitriles, ethers, esters, amides, sulphonamides and carbamates. Finally, a solid-supported version of these catalysts is currently under investigation.References 1) Guillena, G.; Ram�n, D. J.; Yus, M. Chem. Rev. 2010  , 110, 1611.2) Hamid, M. H. S. A.; Slatford, P. A.; Williams, J. M. J. Adv. Synth. Catal. 2007  , 349, 1555.

Hydrogen borrowing methodology: New iridium(III) catalysts for amine alkylation reactions

248th National Meeting (2014)

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