Ni-Catalyzed Reductive Difunctionalization of Alkenes

Abstract

Alkene difunctionalization represents one of the most efficient methods to synthesize highly functionalized molecules from simple and readily available starting materials. In contrast to the well-established redox-neutral alkene difunctionalization reactions, reductive alkene difunctionalization, which simultaneously introduces two electrophiles on both sides of the double bond, has been much less developed, especially in enantioselective manner. This review summarizes recent advances in the nickel-catalyzed reductive difunctionalization of alkenes and highlights the enantioselective transformations.1 Introduction2 Nickel-Catalyzed Racemic Reductive Difunctionalization of Alkenes3 Nickel-Catalyzed Enantioselective Reductive Difunctionalization of Alkenes3.1 Diarylation of Alkenes3.2 Aryl-alkenylation of Alkenes3.3 Aryl-monofluoroalkenylation of Alkenes3.4 Reductive Cyclization/Coupling with Alkynyl Bromides or Asymmetric Internal Alkynes3.5 Aryl-alkylation of Alkenes3.6 Aryl-amination of Alkenes4 Summary and Outlook

Nickel-catalyzed asymmetric reductive aryl-allylation of unactivated alkenes

“…In recent years, the rapid development of transition-metal catalyzed asymmetric aryl-carbofunctionalizations of aryl borane- or aryl (pseudo)halide-tethered alkenes allow the efficient synthesis of chiral benzene-annulated cyclic compounds in a highly enantioselective fashion ( Scheme 1A ). 1 The enantiodetermining step of these reactions relies on facially selective intramolecular Heck-type arylmetallation. After ring closure, the generated chiral alkyl metal species can be intercepted by a boronic acid, an organo(pseudo)halide, a terminal alkyne, or carbon monoxide to deliver the cross-coupling products in either a redox-neutral or a reductive pathway.…”

Nickel-Catalyzed Reductive Asymmetric Aryl-Acylation and Aryl-Carbamoylation of Unactivated Alkenes

“…In the last decade, transition-metal catalyzed enantioselective dicarbofunctionalizations of tethered alkenes has evolved into a reliable method to construct the scaffold of chiral benzene-fused cyclic compounds. [1][2][3][4][5][6] The majority of these reactions relies on a facially selective Heck-type arylmetallation of the pendant olefinic unit as the enantiodetermining step, 7 which is followed by trapping of the generated σ-alkylmetal species with either a nucleophile or an electrophile. Based on this strategy, asymmetric aryl-alkylation, [8][9][10] diarylation, [10][11][12][13] arylbenzylation, 14 aryl-alkenylation 15,16 and aryl-alkynylation 13,17,18 of incorporated alkenes have been developed under palladium, copper or nickel catalysis.…”

Iodine-mediated oxythiolation of o-vinylanilides with disulfides for the synthesis of benzoxazines

“…It is convenient to introduce functional groups into the carbon chain by addition reaction. 1,2 Furthermore, heterocyclic compounds also could be built efficiently from alkenes by addition–cyclization with reasonable design of starting materials. 3–5 For example, benzo[ d ][1,3]oxazine, an essential heterocyclic skeleton which is widely found in natural products and biological active molecule, 6–10 could be synthesized by the intramolecular cyclization of N -(2-(1-phenylvinyl)phenyl)-benzamides (Scheme 1).…”