An unprecedented highly regio- and enantioselective rhodium-catalyzed addition of 1,3-diketones to terminal and 1,1-disubstituted allenes furnishing asymmetric tertiary and quaternary all-carbon centers is reported. By applying a Rh /phosphoramidite/TFA catalytic system under mild conditions, the desired chiral branched α-allylated 1,3-diketones could be obtained in good to excellent yields, with perfect regioselectivity and in high enantioselectivity. The reaction shows a broad functional-group tolerance on both reaction partners highlighting its synthetic potential.
A new method for the rhodium-catalyzed regioselective C-C bond formation using terminal alkynes and 1,3-dicarbonyl compounds to achieve valuable branched α-allylated 1,3-dicarbonyl products is reported. With a Rh(I)/DPEphos/p-CF3-benzoic acid as the catalyst system, the desired products can be obtained in good to excellent yields and with perfect regioselectivity. A broad range of functional groups were tolerated, and first experimental insights of a plausible reaction mechanism were obtained.
The first rhodium‐catalyzed regioselective addition of 1,3‐dicarbonyl compounds, including β‐keto esters, β‐keto amides, and 1,3‐diketones, to internal alkynes furnishes branched allylic compounds. By applying RhI/DPEphos/TFA as the catalytic system, aliphatic as well as aromatic internal methyl‐substituted alkynes act as suitable substrates to yield valuable branched α‐allylated 1,3‐dicarbonyl compounds regioselectively in good to excellent yields. A simple basic saponification–decarboxylation procedure provides access to valuable γ,δ‐unsaturated ketones. The reaction shows a broad functional‐group tolerance, and numerous structural variations on both reaction partners highlight the synthetic potential and flexibility of this method.
An unprecedented highly regio‐ and enantioselective rhodium‐catalyzed addition of 1,3‐diketones to terminal and 1,1‐disubstituted allenes furnishing asymmetric tertiary and quaternary all‐carbon centers is reported. By applying a RhI/phosphoramidite/TFA catalytic system under mild conditions, the desired chiral branched α‐allylated 1,3‐diketones could be obtained in good to excellent yields, with perfect regioselectivity and in high enantioselectivity. The reaction shows a broad functional‐group tolerance on both reaction partners highlighting its synthetic potential.
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