Rhodium-Catalysed Ynamide Carbometallations for Stereoselective Synthesis

Lead Research Organisation: University of Edinburgh
Department Name: Sch of Chemistry


Enamides are compounds that contain a carbon-carbon double bond attached to a nitrogen atom that is itself bonded to an electron-withdrawing functional group. Enamides have recently emerged as versatile synthetic intermediates for a range of useful chemical reactions. However, the synthesis of highly substituted enamides in a fully controlled fashion is often highly challenging, and this limitation hampers full exploration of their chemistry. The proposed research is aimed at the development of a recently discovered reaction that enables the controlled synthesis of highly substituted enamides. This reaction proceeds under mild conditions, and employs a commercially available rhodium complex as a precatalyst along with organozinc compounds as organometallic reagents. A reasonably wide range of enamides can be accessed using this chemistry, and preliminary investigations suggest that these new compounds display useful reactivities in a variety of reactions. However, much more work is required to fully develop the scope of both the enamide synthesis itself, and of the synthetic applications of the enamide products. These objectives are at the heart of this proposal.


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Description The actual research carried out employed rhodium-catalysed carbometallation in a different context from that originally intended. This research resulted in:1. The development of highly enantioselective rhodium-catalysed additions of arylboronic acids to alkenylazaarenes (also called alkenylheteroarenes).2. The development of highly enantioselective rhodium-catalysed cyclisations of arylboronic esters onto ketones.
Exploitation Route The findings from this research may stimulate other academic researchers to develop new methods to make important molecules with even greater efficiency. The methods we have developed may be adopted by synthetic chemists in the pharmaceutical and agrochemical industries to prepare biologically active molecules for use in new medicines or agrochemicals.
Sectors Chemicals,Pharmaceuticals and Medical Biotechnology