Visible-Light-Induced Decarboxylative Alkylation/Ring Opening and Esterification of Vinylcyclopropanes

Abstract

A visible-light-induced four-component reaction of vinylcyclopropanes, N-(acyloxy)­phthalimide esters, N,N-dimethylformamide (DMF), and H2O through an oxidative ring opening of cyclopropane is presented. This procedure provides a new and effective way to construct formate esters. DMF is employed as both a solvent and the source of CHO. This difunctionalization of vinylcyclopropanes shows good functional group tolerance under room temperature. A radical pathway is involved, and carbonyl oxygen of ester originated from water in this transformation.

Molybdenum-Mediated Reductive Hydroamination of Vinylcyclopropanes with Nitroarenes: Synthesis of Homoallylamines

“…On the basis of our mechanistic findings and previous literatures, , we propose a plausible reaction pathway for this molybdenum-mediated reductive hydroamination of VCPs (Scheme ). Initially, the olefinic bond of the VCP coordinates to molybdenum to form intermediate A .…”

“…Transition-metal-catalyzed cycloaddition of VCPs with various π systems, including alkenes and alkynes as well as some carbon–heteroatom systems such as ketones, aldehydes, and imines, has been well-developed . Meanwhile, the transition-metal-catalyzed ring openning of VCPs is another important reaction mode of VCPs to access allylic compounds and has become an increasingly popular research field (Scheme b) . For example, in 2007 Togni reported a gold­(I)-catalyzed ring-opening reaction of unactivated VCPs with sulfonamides to afford useful homoallylic amine derivatives .…”

Alkoxy Radical Induced Transformations from N‐Alkoxyphthalimides Under the Photoredox Catalysis

“…The wide substrate scope could tolerate α-heteroatom-activated CÀ H bonds, such as paramethoxy, para-fluoro, and ortho-iodo substituents (10)(11)(12). Other aromatic rings were also utilized for this reaction, including thiophene, pyridine, and indole (14)(15)(16). Beyond the aromatic stabilization system, aliphatic tertiary carbon could furnish the adduct product efficiently (17)(18)(19)(20).…”

“…Meanwhile, in view of the enormous transformations from its carboxylic acid analogous, it is surprising to note that the chemistry of alkoxy radicals, has not attained the same degree of importance [12–15] . The analogous radical chemistry of carboxylic acid and its derivatives has been investigated much more widely, and this topic has been extensively reviewed [16–24] .…”

“…[6][7][8][9][10][11] Meanwhile, in view of the enormous transformations from its carboxylic acid analogous, it is surprising to note that the chemistry of alkoxy radicals, has not attained the same degree of importance. [12][13][14][15] The analogous radical chemistry of carboxylic acid and its derivatives has been investigated much more widely, and this topic has been extensively reviewed. [16][17][18][19][20][21][22][23][24] Mechanistically, the radical pathway for carboxylic acid counterpart was mainly the decarboxylative process followed by crosscoupling for diverse carbon-carbon and carbon-heteroatom bond construction with extruding carbon dioxide as a traceless leaving group.…”