A copper-catalyzed four-component reaction of arylcyclopropanes, nitriles, carboxylic acids and N-fluorobenzenesulfonimide: facile synthesis of imide derivatives

Abstract

An unprecedented copper-catalyzed four-component reaction of arylcyclopropanes, nitriles, carboxylic acids and N-fluorobenzenesulfonimide (NFSI) has been successfully developed, which represents the first example of four-component reaction of non-Donor-Acceptor cyclopropanes. A wide...

Electrochemical 1,3-Alkyloxylimidation of Arylcyclopropane Radical Cations: Four-Component Access to Imide Derivatives

“…Supported by the above-depicted control experiments, cyclic voltammetry results, and previous reports about the cyclopropane-derived radical cation, − we proposed the reasonable reaction mechanism shown in Scheme . This four-component protocol begins with the direct anodic single electron oxidation of arylcyclopropanes 1a to deliver the key radical cation I , which is quickly captured by nucleophilic MeO – generated from the cathodic reduction of MeOH to produce benzyl radical intermediate II .…”

“…9 In this context, Zhang and co-workers developed an unprecedented coppercatalyzed radical-cation-mediated four-component ring-opening 1,3-difunctionalization of arylcyclopropanes, carboxylic acids, nitriles, and N-fluorobenzenesulfonimide (NFSI) (Scheme 1b). 9 In this project, the formation of an arylcyclopropane radical cation relied on the oxidation of a nitrogen-centered radical generated from NFSI. However, a transition-metal catalyst and strong basic conditions were indispensable for this reaction to proceed smoothly.…”

“…Three-component radical-cation-mediated ring-opening 1,3-difunctionalizations of arylcyclopropanes with two nucleophiles have been well established. − In sharp contrast, the similar oxidative four-component ring-opening 1,3-difunctionalization reactions initiated by arylcyclopropane-derived radical cations are still extremely rare due to the difficulties of accurately controlling the reactivity and chemo- and regioselectivity of each reaction component . In this context, Zhang and co-workers developed an unprecedented copper-catalyzed radical-cation-mediated four-component ring-opening 1,3-difunctionalization of arylcyclopropanes, carboxylic acids, nitriles, and N -fluorobenzenesulfonimide (NFSI) (Scheme b) . In this project, the formation of an arylcyclopropane radical cation relied on the oxidation of a nitrogen-centered radical generated from NFSI.…”

Oxidative Imidation of Benzylic and Cycloalkane C(sp3)–H Bond Donors Using N-Aroyloxyquinuclidinium Salts and Nitriles under Photoredox Catalysis

“…Interestingly, carboxylic acid amides fully outcompete carboximides in direct oxidative N–H alkylation with alkanes . Some of the most versatile methods for the preparation of N -alkylimides employing C–H functionalization are based on Ugi–Mumm-type multicomponent oxidative C–C coupling of C–H bond donors, isonitriles, and carboxylic acids. − An example of this chemistry is given in Scheme c where benzoyl peroxide serves as an oxidant and a source of carboxylate . Considering preparation of N -alkylimides via C­(sp 3 )–H functionalization, only a limited number of examples of oxidative C–N coupling of alkanes have been reported, , and no methods for multicomponent oxidative C­(sp 3 )–H imidation have been developed.…”

“…18 Interestingly, carboxylic acid amides fully outcompete carboximides in direct oxidative N−H alkylation with alkanes. 22 Some of the most versatile methods for the preparation of N-alkylimides 23 employing C−H functionalization are based on Ugi−Mumm-type multicomponent oxidative C−C coupling of C−H bond donors, isonitriles, and carboxylic acids. 24−27 An example of this chemistry is given in Scheme 1c where benzoyl peroxide serves as an oxidant and a source of carboxylate.…”