Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†

Abstract

As a straightforward strategy for rapidly increasing molecular complexity, dicarbofunctionalization of alkenes has attracted substantial interests of organic synthesis, medicine chemistry, and materials science. Nickel-catalyzed cascade dicarbofunctionalizations have been flourished in this area recently, and nickel-mediated radical pathways particularly offer new opportunities in conjunctive cross-couplings with alkyl coupling partners. Herein, we give a comprehensive review of nickel-catalyzed dicarbofunctionalization of alkenes through a historical perspective, including intermolecular three-component reactions and intramolecular cascade reactions. Among the pathways discussed in this review, the carbometallation/cross-coupling process and the radical addition/cross-coupling process are the two major pathways for the nickel-catalyzed dicarbofunctionalization of alkenes. The oxidative cyclization and 1,2-metallate shift processes are also selectively discussed. These methods overcome the limitations associated with the reactions using noble metals in the field, providing an efficient and straightforward access to structurally diversified molecules. Yun-Cheng Luo (right) received his BSc degree in 2016 and master degree in 2019 from University of Science and Technology of China. Then he joined Professor Xingang Zhang's group at Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences to pursue his doctorate in organic chemistry. His research interests are focused on the activation of inert C-H or C-X bonds of bulky chemicals and their applications in the synthesis of fluorine-containing compounds. Chang Xu (middle) obtained his BSc degree in basic pharmacy from China Pharmaceutical University (China) in 2015. With an interest in organic chemistry and medicinal chemistry, he then began his graduate studies at Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences under the supervision of Professor Xingang Zhang. His research interests are focused on the activation and transformations of fluoroalkylanes and their applications in medicinal chemistry. Xingang Zhang (left) obtained his BSc degree in 1998 from Sichuan University (China) and received the Ph.D. in 2003 at Shanghai Institute of Organic Chemistry (SIOC), Chinese Academy of Sciences. After his postdoctoral work at University of Illinois at Urbana Champaign (USA), he joined the faculty team of SIOC as a research associate professor in 2008, and became research professor in 2012. His current research interests are focused on organofluorine chemistry and chemical biology.

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.…”

Asymmetric three-component olefin dicarbofunctionalization enabled by photoredox and copper dual catalysis

“…Alkenes are arguably one of the most privileged and versatile chemicals in organic synthesis because a diverse range of functional groups could be readily introduced across the C = C π system by many classic vicinal difunctionalization reactions 1 – 4 . In this context, one of the most investigated and fundamental transformations is the intermolecular three-component alkene vicinal dicarbofunctionalization (DCF) reaction, which allows installation of two different carbon fragments.…”

Nickel-Catalyzed Regio- and Diastereoselective Arylamination of Unactivated Alkenes

“…Subsequent 1,2-migratory insertion followed by a sequential electrophilic amination reaction will yield the arylamination product. [34][35][36][37][38][39] Critical to the success of this process, the reaction must be initiated by a transmetalation step to form the Ni-Ar species, which is rarely reported and challenging because of the fact that most of three-component difunctionalization reactions utilizing arylboron reagents were initiated by oxidative addition with electrophiles to Ni(0) catalyst, thus furnishing products that incorporate electrophile at the terminal position and aryl at the internal position. Herein, we reported a new approach for the 1,2-arylamination of unactivated alkenes under practical and easily handled Ni(II) catalytic system with commercial available arylboronic acids and readily prepared Obenzoylhydroxylamines with excellent regio-and diastereocontrol (Fig.…”