ABSTRACT
We describe a 1,2-alkylboration of 3-alkylidene-2-oxindoles with a diboron reagent and alkyl bromides and iodides enabled by copper/bisphosphine catalysis. This scalable alkylboration method provides facile access to 3,3'-dialkyloxindole boronic esters featuring an all-carbon quaternary stereocenter and an increased F(sp3) fraction. In addition to good functional group tolerance and prolific utilization of drug/pesticide-derived alkyl iodides, the conversion of the C-B bond to a C-C/C-X bond offers further opportunities for structural variation of 3,3'-dialkyloxindoles.
ABSTRACT
We describe a novel, regioselective alkylboration of versatile (hetero)benzylidenecyclopropanes with ß-H-containing alkyl iodides and bis(pinacolato)diboron enabled by copper catalysis. This three-component method allows for consecutive B-Csp3 and Csp3-Csp3 bond formation to access Csp3-enriched diverse tertiary cyclopropyl boronic esters with broad functionality tolerance, and the so-formed C-B bond is amenable to further structural diversification. Radical clock experiment, Hammett analysis, and DFT calculation suggest a mechanism of polar, rather than radical manifold, and SN2-type C-C bond formation was found to be the rate-limiting step instead of migratory alkene insertion.
