Aminoquinoline-directed, cobalt-catalyzed carbonylation of sulfonamide sp² C–H bonds

Abstract

We report a method for cobalt-catalyzed, aminoquinoline-directed sp2 C–H bond carbonylation of sulfonamides. The reactions proceed in a dichloroethane solvent, and employ diisopropyl azodicarboxylate as a carbon monoxide source, Mn(OAc)2 as a cooxidant and potassium pivalate as a base. Halogen, ester, and amide functionalities are compatible with the reaction conditions. This method allows for a short and efficient synthesis of saccharin derivatives.

A comprehensive overview of directing groups applied in metal-catalysed C–H functionalisation chemistry

“…The last example was published by Daugulis in 2017, also using DIAD and a Co-based catalytic system, for the carbonylation of sulfonamide derivatives ( Scheme 71D ). 442 This reaction gave easy access to 2-sulfobenzoic acid imides in moderate to good yields (47–73%).…”

Switching the site-selectivity of C–H activation in aryl sulfonamides containing strongly coordinating N-heterocycles

“…2A). [44][45][46] In this study, we successfully switched the selectivity of the C-H carbenoid functionalization 47-66 of sulfonamides [67][68][69][70][71][72][73][74][75][76][77][78][79][80] containing N-heterocycles 81 using a rhodium catalyst. The selectivity was precisely controlled by changing the reaction medium polarity and additive concentration, affording C-H activation at the ortho position relative to the N-heterocycle (charge-neutral forms, denoted as L-type ligands) or sulfonamide (easily deprotonated to charge-negative forms, denoted as X-type ligands) directing groups.…”

Rhodium‐Catalyzed C(sp2)‐ or C(sp3)−H Bond Functionalization Assisted by Removable Directing Groups

“…[195][196][197] As ar esult of the ease of transforming sulfonic acids into sulfonamides,t he majority of directed CÀH activation studies have been focused on the use of sulfonamide derivatives.I nf act, catalytic reactions of sulfonamides with various coupling partners represent ah ighly explored field. [198][199][200][201][202][203] Herein, we review Rh-catalyzed sulfonamide CÀHf unctionalizations without addressing the issue of the directing group moiety.…”