A highly stereoselective synthesis of thiocyanated enaminones was achieved by an electrochemical process, which involved C–H bond thiocyanation and vinyl C–N bond transamination.
China XD Group (China)
Publishes on Catalytic C–H Functionalization Methods, Catalytic Cross-Coupling Reactions, Chemical Synthesis and Analysis. 10 papers and 106 citations.
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A highly stereoselective synthesis of thiocyanated enaminones was achieved by an electrochemical process, which involved C–H bond thiocyanation and vinyl C–N bond transamination.
)-H sulfuration has been developed. Various enaminones and thiophenols were compatible, generating the desired alkenyl sulfur compounds in up to 87 % yield. This transformation proceeded smoothly under mild reaction conditions without external oxidant and transition-metal catalyst. Remarkably, thiophenols selectively coupled with enamines when substrates had other alkenyl groups. In addition, the desired products could be further transformed into a series of α-sulfur isoxazoles, which are a kind of useful heterocycles in materials and bioactive molecules.
The transmetalation as the rate-limiting step was effectively accelerated by newly designed N-heterocyclic carbenes with triazine wingtips (T-NHC). By using a ppm-level precatalyst T-NHC-Pd (8), the highly efficient coupling of aryl iodide, alkyne and carbon monoxide furnished a variety of ynone compounds. T-NHC-Pd (5), which deprotonated 4-methyl-phenylacetylene under mild conditions, converted into alkynyl-coordinated catalytic active species PdCl(T-NHC)(Py)(alkynyl). In the putative Pd/Pd catalytic cycle, both triazine-wingtips and NHCs are key players for establishing the carbonylative cross-couplings with high TON and TOF.
Benzodiazepines are essential structural motifs commonly found in biologically active compounds and pharmaceutical agents.