Regioselective Electrochemical Construction of Csp2-Csp2 Linkage at C5-C5' Position of 2-Oxindoles via an Intermolecular Anodic Dehydrogenative Coupling.

Applying electricity as a reagent in synthetic organic chemistry has attracted particular attention from synthetic chemists worldwide as an environmentally benign and cost-effective technique. Herein, we report the construction of the Csp2-Csp2 linkage at the C5-C5' position of 2-oxindole utilizing electricity as the traceless oxidant in an anodic dehydrogenative homo-coupling process. A variety of 3,3-disubstituted-2-oxindoles were subjected to dimerization, achieving yields of up to 70% through controlled potential electrolysis at an applied potential of 1.5 V versus Ag/Ag+ nonaqueous reference electrode. This electro-synthetic approach facilitates the specific assembly of C5-C5' (para-para coupled) dimer of 3,3-disubstituted-2-oxindole without the necessity of any external oxidants or additives and DFT (Density Functional Theory) calculations provided confirmation of this pronounced regioselectivity. Furthermore, validation through control experiments and voltammetric analyses substantiated the manifestation of radical-radical coupling (or biradical pathway) for the dimerization process.

Total Synthesis of (+)- and (-)-Calycanthine by Means of Thio-Urea-Catalyzed Sequential Michael Reactions of Bis-oxindoles.

A unified catalytic asymmetric approach to naturally occurring piperidinoindoline and pyrrololidinoindoline alkaloids has been realized via the development of a thio-urea-catalyzed sequential Michael addition of bis-oxindole onto nitroethylene (up to 93% ee and >20:1 dr). This strategy offers the total syntheses of either enantiomers of naturally occurring calycanthine.

Concise total syntheses of bis(cyclotryptamine) alkaloids via thio-urea catalyzed one-pot sequential Michael addition.

Naturally occurring bis(cyclotryptamine) alkaloids feature vicinal all-carbon quaternary stereocenters with an elongated labile C-3a-C-3a' Sigma bond with impressive biological activities. In this report, we have developed a thio-urea catalyzed one-pot sequential Michael addition of bis-oxindole onto selenone to access enantioenriched dimeric 2-oxindoles with vicinal quaternary stereogenic centers at the pseudobenzylic position (up to 96% ee and >20 : 1 dr). This strategy has been successfully applied for the total syntheses of either enantiomers of chimonanthine, folicanthine, and calycanthine.