RESUMEN
Using 2-diazo-3,3,3-trifluoropropanoate as a nontraditional two-carbon reaction partner, a Rh(III)-catalyzed defluorinative [4 + 2] annulation for the synthesis of 1,3,4-functionalized isoquinolines was developed. The reaction proceeds by sequential C-H carbenoid insertion, dual C-F bond cleavage/annulation, and N- to O-sulfonyl migration. The resultant products were converted to diverse 1,3,4-trisubstituted isoquinolines based on the functionalization of the newly installed 1-sulfonate, 2-fluoro functional handles, and/or remaining ester motif.
RESUMEN
The fragmentation of N-acyl-isoxazol-5-ones using visible light photoredox catalysis has been disclosed. The catalyst-controlled divergent mechanisms, namely the oxidative and reductive quenching catalytic cycle, are utilized. Various oxazoles and 1,3-oxazin-6-ones are selectively obtained from the same isoxazol-5-one skeleton under mild conditions.
RESUMEN
A blue light-promoted cross-coupling of two distinct diazo compounds was described. The reaction produces E-configured trisubstituted alkenes in good yields in the absence of catalysts and additives. The reactive free carbene intermediates were generated via selective photolysis of one of the two diazo compounds upon blue light irradiation.
RESUMEN
A photoredox approach to generate distal cyano-substituted alkyl radicals through C-C bond cleavage of cyclobutanone oximes was developed. The radicals produced by this method were applied to three-component cyanopropylation/etherification of unactivated alkenes. Their reactions with diverse radical acceptors were also demonstrated.
