Ni(I)-Catalyzed β,δ-Vinylarylation of γ,δ-Alkenyl α-Cyanocarboxylic Esters via Contraction of Transient Nickellacycles

Dhungana, Roshan K.; Kc, Shekhar; Basnet, Prakash; Aryal, Vivek; Chesley, Lucas J.; Giri, Ramesh

doi:10.1021/acscatal.9b03574

Cited by 46 publications

(21 citation statements)

References 70 publications

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“…In 2019, the Giri group also disclosed a transmetallation‐initiated nickel‐catalyzed β,δ‐vinylarylation of γ,δ‐alkenyl α‐cyanocarboxylic esters with vinyl triflates and arylzinc reagents (Scheme 28). [ 80 ] The acidic α‐H of α‐cyanocarboxylic ester was essential to promote the reaction, suggesting that the Ni species involved in the catalytic cycle were stabilized as Ni‐enolates. The non‐classical 3,1‐regioselectivity was ascribed to the contraction of the nickelacycles from six‐membered to five‐membered ring.…”

Section: Intermolecular Dicarbofunctionalization Of Alkenesmentioning

confidence: 99%

Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†

2020

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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.

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Section: Intermolecular Dicarbofunctionalization Of Alkenesmentioning

confidence: 99%

Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†

2020

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“…Very recently, the Giri group further expanded the weak directing groups to cyanocarboxylic esters, and developed the three-component, regioselective ,-vinylarylation of alkenyl esters with vinyl triflates and arylzinc reagents through a nickel-enabled metallacycle contraction process that had been previously reported (Scheme 10). 11 The reaction proceeded well with good compatibility of arylzinc reagents and vinyl triflates, installing the vinyl group on the -position of esters and the aryl group on the -position with complete regioselectivity. The presence of both the cyano and ester functional groups turned out to be essential for the desired reactivity.…”

Section: Short Review Syn Thesismentioning

confidence: 89%

Recent Advances in Nickel-Catalyzed Three-Component Difunctionalization of Unactivated Alkenes

Tu¹,

Zhu

Qing³

et al. 2020

Synthesis

124

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Catalytic, intermolecular difunctionalization of alkenes represents an efficient and diverse protocol for the buildup of molecular complexity from abundant materials by forging two chemical bonds in a single operation. Despite important progress in this area, transition-metal-catalyzed three-component difunctionalization of unactivated alkenes remains underdeveloped, mainly because of the low reactivity, reduced polarization, and high tendency toward β-hydride elimination of these compounds. In this context, nickel-catalyzed, selective, intermolecular difunctionalization methods that generally proceed via two distinct reaction pathways, migratory insertion of nickel species into alkenes and radical addition to alkenes, have been developed. This short review highlights recent advances in this area.1 Introduction2 Nickel-Catalyzed Three-Component Difunctionalization of Unactivated Alkenes via Migratory Insertion Processes3 Nickel-Catalyzed Three-Component Difunctionalization of Unactivated Alkenes via Radical Processes4 Conclusions and Perspectives

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“…12C). 33 The optimal conditions for this b,d-vinylarylation use 5 mol% NiCl 2 and 1.5 equiv. of both KPF 6 and 4-phenylpyridine (4-PhPy).…”

Section: Non-conjugated Alkene Substratesmentioning

confidence: 99%

Recent developments in nickel-catalyzed intermolecular dicarbofunctionalization of alkenes

et al. 2020

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Ni(I)-Catalyzed β,δ-Vinylarylation of γ,δ-Alkenyl α-Cyanocarboxylic Esters via Contraction of Transient Nickellacycles

Cited by 46 publications

References 70 publications

Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†

Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†

Recent Advances in Nickel-Catalyzed Three-Component Difunctionalization of Unactivated Alkenes

Recent developments in nickel-catalyzed intermolecular dicarbofunctionalization of alkenes

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Ni(I)-Catalyzed β,δ-Vinylarylation of γ,δ-Alkenyl α-Cyanocarboxylic Esters via Contraction of Transient Nickellacycles

Cited by 46 publications

References 70 publications

Nickel‐CatalyzedDicarbofunctionalization of Alkenes†

Nickel‐CatalyzedDicarbofunctionalization of Alkenes†

Recent Advances in Nickel-Catalyzed Three-Component Difunctionalization of Unactivated Alkenes

Recent developments in nickel-catalyzed intermolecular dicarbofunctionalization of alkenes

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Product

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Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†

Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†