Nickel-catalyzed asymmetric reductive aryl-allylation of unactivated alkenes

Abstract

Herein we report a nickel-catalyzed asymmetric reductive aryl-allylation of aryl iodide-tethered unactivated alkenes, wherein both acyclic allyl carbonates and cyclic vinyl ethylene carbonates can serve as the coupling partners. Furthermore,...

Enantioselective Reductive Divinylation of Unactivated Alkenes by Nickel-Catalyzed Cyclization Coupling Reaction

“…The majority of reports have focused on the reactions of aryl-tethered alkenes, in which the rigid aromatic ring is incorporated to improve the selectivity (Scheme a). Over the past few years, studies along these lines have progressed significantly, with the scope expanded from single-molecule to two-component reactions, from activated substrates , to unactivated alkenes, , and from nucleophile–electrophile reactions , to cross-electrophile couplings. , In short contrast, the reactions of nonaromatic substrates remain elusive, and the major advances have been limited to carbamoyl-tethered alkenes for producing chiral pyrrolidinone (Scheme b) . The development of new tethered alkenes for asymmetric dicarbofunctionalizations is essential for improving the structural diversity of chiral cyclic compounds.…”

Ni-Catalyzed Reductive Arylcyanation of Alkenes

“…We and other groups have developed a Ni-catalyzed alkene dicarbofunctionalization reaction through intramolecular Heck cyclization followed by intermolecular cross-coupling . A series of carbon electrophiles, including aryl halides, alkenyl halides, alkynyl halides, alkyl halides, CO 2 , trifluoromethylalkenes, etc., have been successfully installed (Scheme b). To continue our study in Ni-catalyzed dicarbofunctionalization of alkenes for the construction of heterocycles bearing all-carbon quaternary centers, we herein disclose a Ni-catalyzed reductive arylcyanation of alkene for the preparation of cyano-substituted oxindoles and isoquinoline-1,3-diones using NCTS as the organo cyanating reagent (Scheme c) …”

Synthesis of 3,3-Dialkyl-Substituted Isoindolinones Enabled by Nickel-Catalyzed Reductive Dicarbofunctionalization of Enamides

“…The Ni-catalyzed difunctionalization of alkenes has been proven as a useful approach to rapidly increase molecular complexity . Particularly, asymmetric reductive difunctionalization, which circumvents the use of preprepared and unstable organometallic nucleophiles, has emerged as a powerful strategy with high functionality tolerance. , Recently, Ni-catalyzed asymmetric intramolecular difunctionalization of 1,1-disubstituted alkenes consisting of a cyclization/reductive cross-coupling cascade has become a convenient synthetic platform to obtain various benzo-fused rings with a tetrasubstituted stereocenter . In view of the fact that enamide is regarded as an important and multipurpose nitrogen-containing building bock, , which has been widely used in transition-metal catalyzed asymmetric functionalization reactions to forge multifarious chiral amines and enamides derivatives, , we hypothesized that Ni-catalyzed cyclization via intramolecular insertion of a 1,1-disubstituted enamide led to the amide derivatives holding a tetrasubstituted carbon center.…”

“…Relying on the previous research on the nickel-catalyzed cyclization/reductive coupling reaction, a plausible mechanism is illuminated in Figure . Initially, Ni(0) undergoes oxidative addition with enamide 1a to generate the aryl Ni­(II) species A , which successively accomplishes the enantioselective migratory insertion to produce species B .…”