Metal-free, visible-light-promoted decarboxylative alkylation of Baylis–Hillman acetates withN-(acyloxy)phthalimides

Abstract

A visible light-driven metal- and oxidant-free procedure for the decarboxylative alkylation of Baylis–Hillman acetates with N-(acyloxy)phthalimides to access trisubstituted alkyl acrylates under mild reaction conditions is reported.

Phthalimides: developments in synthesis and functionalization

“…Metal-free synthesis of phthalimide derivatives can be carried out under organocatalysis, base catalysis, or acid catalysis methods. [57][58][59][60][61] Compared to transition metal catalysts, these methods offer a greener appeal. For example, organocatalysis approaches are readily available, cost-effective, low toxic, environmentally friendly and insensitive to moisture or oxygen, which makes them a suitable and promising route for preparing pharmaceuticals over metal catalysts.…”

Photoinduced Alkylsulfonylation and Cyanoalkylsulfonylation of Morita–Baylis–Hillman Adducts via Multicomponent Insertion of Sulfur Dioxide

“…Significantly, MBH adducts can be served as an excellent radical acceptor in organic synthesis since their distinctive structures incorporate an activated CC bond connected to electron-withdrawing groups. A great deal of radical donors, such as Langlois’ reagent, N -hydroxyphthalimide esters (NHPI esters), potassium organotrifluoroborates, tertiary amines, ethers, α-bromo ketones, or NHC-boranes have been proved to be ideal C or B-radical precursors under photoredox catalysis or electrocatalysis to provide numerous trisubstituted olefins (Scheme a). In addition, the aryl sulfonylation of MBH adducts has been identified as an efficient method to obtain allylic sulfones by exploiting various sulfonyl reactants .…”

Zn-Mediated Fragmentation of N-Alkoxyphthalimides Enabling the Synthesis of gem-Difluoroalkenes

“…Recently, alkyl radicals generated by single-electron transfer (SET) from zero-valent metal to N -(acyloxy)­phthalimides (NHPIs) have been employed in several useful transformations under mild conditions. − Baran et al have developed a Zn nanopowder-promoted Giese reaction on DNA for the synthesis of C­(sp 3 )–C­(sp 3 ) linkages on DNA. Our group has successfully achieved the decarboxylative/defluorinative alkylation of α-trifluoromethyl alkenes with NHPIs to build various gem -difluoroalkenes in the presence of Zn powder.…”