RESUMEN
A RhII -catalyzed method for intermolecular alkylation of the ß-C(sp2 )-H bond of enol ethers, enamides, and enecarbamates with α-diazo-1,3-dicarbonyl compounds is reported. The products are formed in up to 99 % yield and can be readily derivatized under a variety of conditions. By utilizing a combination of experimental and computational studies, the presumptive addition-elimination reaction mechanism was investigated and found to proceed under thermodynamic control at higher temperature. The acquired fundamental knowledge was translated into a strategic reaction design and yielded the first example of the ß-C-H functionalizations of acyclic enol ethers using α-diazo-1,3-dicarbonyl compounds.
RESUMEN
A bis(phosphine)/triflatosilyl pincer-type Rh(i) complex can reversibly store one equivalent of H2 across the Si-Rh bond upon triflate migration from silicon to rhodium. The triflatosilyl complex serves as an effective precatalyst for norbornene hydrogenation, but Si-OTf bond cleavage is not implicated in the major catalytic pathway. The combined findings suggest possible strategies for M/Si cooperation in catalytic processes.
