Pd-Catalyzed enantioselective synthesis of 2-methyl-3-methyleneindoline

Recent Advances in Metal‐Catalyzed Decarboxylative Reactions of Vinyl Benzoxazinanones

“…In 2021, Li's group reported an enantioselective Pd‐catalyzed 2‐methyl‐3‐methyleneindoline synthesis from racemic vinyl benzoxazinones with the help of ( R , R )‐BenzP* (Scheme 6). [10] They reported the Pd‐catalyzed enantioselective synthesis of 2‐methyl‐3‐methyleneindoline ( 16 ) in up to 89% yield and 84% ee with ( R , R )‐BenzP* as the chiral ligand. The β ‐hydride elimination provided a new reaction pathway besides migratory insertion to benzyne (Zhai's work), which inspired us to explore further transformation for the palladacyclobutane structure.…”

Iridium-Catalyzed Intramolecular Asymmetric Allylation of Vinyl Benzoxazinones for the Synthesis of Chiral 4H-3,1-Benzoxazines via Kinetic Resolution

“…In recent years, vinyl benzoxazinones have attracted considerable attention in the field of organic synthesis, with the formation of π-allyl-metal species via the decarboxylation process, which have always been considered as an array of competent reactants for catalytic asymmetric cyclizations . After Tunge’s pioneering research work, significant contributions have been made by Xiao and co-workers, Glorius and co-workers, and others, with most of these catalytic transformations based on the above π-allyl-metal species with C,N-1,4 four-atom building blocks in various [4 + n ]-cycloadditions to access different ring-size heterocyclics. In comparison to these catalytic cycloadditions of vinyl benzoxazinones, asymmetric catalytic synthesis of chiral benzoxazinones have rarely been explored.…”

Palladium-Catalyzed Asymmetric Cascade Intramolecular Cyclization/Intermolecular Michael Addition Reaction of Allenyl Benzoxazinones with 1-Azadienes

“…The strategies to access N-heterocyclic compounds have drawn great attention; among them, palladium-catalyzed decarboxylative cycloaddition reactions are powerful synthetic tool . Recently, vinyl benzoxazinones have emerged as versatile blocks for constructing nitrogenous skeletons. , As shown in Scheme , in the presence of a palladium catalyst, vinyl benzoxazinone leads to a π-allyl Pd-intermediate bearing a N-nucleophile, and the zwitterion could undergo four paths (a–d) to form N-heterocycles. Path a is well developed, and numerous reagents, such as electron-deficient olefins, sulfur-ylides, enals, ketenes, isatins, carboxylic acids, sulfonyl isocyanates, imines, [60]­fullerene, deconjugated butenolides, and 1,3-dipoles, have been involved in this type of reaction .…”