A method for alkylating the β-C(sp<sup>2</sup>)-H bond of cyclic and acyclic enol ethers and enamides via Rh(II) carbenes generated from α-diazo dicarbonyls is reported. This method is not only compatible with the well-studied dimethyl diazo malonate, but also features β-amide and β-keto ester diazo compounds yielding products in up to 99%. Such substrate tolerance affords an efficient and intermolecular route to synthetically malleable β,γ-unsaturated dicarbonyls with structurally interesting subunits such as the indole, thiophene, and Weinreb amide moieties. DFT calculations support a previously proposed addition-elimination pathway in which the alkene adds asynchronously to the electrophilic rhodium carbene and intramolecular proton abstraction preempts cyclopropane formation.

Rh(II) catalyzed C(sp<sup>2</sup>)-H alkylation of enol ethers and enamides: Furnishing β,γ-unsaturated 1,3-dicarbonyls

251st National Meeting (2016)

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Rh(II) catalyzed C(sp2)-H alkylation of enol ethers and enamides: Furnishing β,γ-unsaturated 1,3-dicarbonyls

Rh(II) catalyzed C(sp²)-H alkylation of enol ethers and enamides: Furnishing β,γ-unsaturated 1,3-dicarbonyls