Rh(II)-Catalyzed β-C(sp2)-H Alkylation of Enol Ethers, Enamides and Enecarbamates with α-Diazo Dicarbonyl Compounds

Brett McLarney, Marchello A Cavitt, Djamaladdin G. Musaev, Theodore Donnell, Stefan Anthony France

Chemistry, A European Journal,
2016, Advance Article; DOI: 10.1002/chem.201604518

11/2016

In this collaboration between the France (GA Tech) and Musaev (Emory) groups the dirhodium-catalyzed beta-(Csp2)–H functionalization of enol ethers, enamides and enecarbamates with acceptor/acceptor carbenes is reported. The reaction is highly efficient and the products are demonstrated to be versatile intermediates for further synthetic elaboration.

Using a combination of experimentals and computational studies the presumptive addition-elimination reaction mechanism was explored, findings from which were translated into reaction design, affording the first successful example of the beta-C–H functionalization of acyclic enol ethers using the acceptor carbene systems.

This transformation represents a significant expansion in the scope of substrates for carbene C–H insertion chemistry for future exploitation.

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