Nickel-Catalyzed Difunctionalization of Unactivated Alkenes Initiated by Unstabilized Enolates

Huang, David; Olivieri, Diego; Sun, Yang; Zhang, Pengpeng; Newhouse, Timothy R.

doi:10.1021/jacs.9b09245

Cited by 42 publications

(17 citation statements)

References 64 publications

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“…These reactions, still difficult to develop, intrinsically minimize the number of catalytically generated alkylmetal species prone to undergo β-H elimination. A few reports on alkene alkylarylation have also been disclosed (Scheme D), but these reactions mostly utilize tert -alkyl and perfluoroalkyl halides, and α-haloesters amenable to the formation of alkyl, difluoroalkyl, and α-alkoxycarbonylalkyl radicals . Reactions with these reagents bypass the generation of additional β-H–C(sp 3 )–[M] intermediates …”

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confidence: 99%

Ni-Catalyzed Regioselective 1,2-Dialkylation of Alkenes Enabled by the Formation of Two C(sp³)–C(sp³) Bonds

et al. 2020

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We disclose a Ni-catalyzed vicinal difunctionalization of alkenes with benzyl halides and alkylzinc reagents, which produces products with two new alkyl–alkyl bonds. This alkene dialkylation is effective in combining secondary benzyl halides and secondary alkylzinc reagents with internal alkenes, which furnishes products with three contiguous all-carbon secondary stereocenters. The products can be readily elaborated to access complex tetralene, benzosuberene, and bicyclodecene cores. The reaction also features as the most efficient alkene difunctionalization process to date with catalyst loadings down to 500 ppm and the catalytic turnover number (TON) and turnover frequency (TOF) registering up to 2 × 103 and 165 h–1 at rt, respectively.

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confidence: 99%

Ni-Catalyzed Regioselective 1,2-Dialkylation of Alkenes Enabled by the Formation of Two C(sp³)–C(sp³) Bonds

et al. 2020

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“…In 2019, the Newhouse group developed a ketone enolates initiated, nickel‐catalyzed intramolecular dicarbofunctionalization of unactivated alkenes (Scheme 52). [ 122 ] An electron‐deficient phosphine ligand and the additive tetrabutylammonium salt were critical in promoting the reaction. This method enabled efficient access to various bicyclic architectures with a diverse range of (hetero)aryl and alkenyl electrophiles, including many biologically and pharmaceutically relevant scaffolds.…”

Section: Intramolecular Dicarbofunctionalization Of Alkenes Via Cyclimentioning

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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“…[ 11 ] However, metal catalysts or organic solvents are usually necessary for the bifunctionalization of olefins, which virtually increases the cost and the risk of environmental pollution (Scheme 1a). [ 12 ] Therefore, there is still great demand for the development of some green and cheap difunctionalization reaction systems to afford functional compounds of great importance.…”

Section: Introductionmentioning

confidence: 99%

An efficient transition metal‐free difunctionalization of alkenes in water for the green preparation of sulfone compounds

Yang

Wang

Nie

et al. 2021

Applied Organom Chemis

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A direct difunctionalization method of alkenes with quinoxalin-2(1H)-ones and sodium sulfonates toward sulfone derivatives has been developed under environmentally friendly conditions. This strategy represents an efficient and practical difunctionalization of olefins using water/aqueous media as a sustainable solvent. In addition, this transition metal-free reaction is high yield, and operationally simple, and in particular, proceeds under mild conditions to afford desired sulfones with high functional group compatibility.

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Nickel-Catalyzed Difunctionalization of Unactivated Alkenes Initiated by Unstabilized Enolates

Cited by 42 publications

References 64 publications

Ni-Catalyzed Regioselective 1,2-Dialkylation of Alkenes Enabled by the Formation of Two C(sp³)–C(sp³) Bonds

Ni-Catalyzed Regioselective 1,2-Dialkylation of Alkenes Enabled by the Formation of Two C(sp³)–C(sp³) Bonds

Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†

An efficient transition metal‐free difunctionalization of alkenes in water for the green preparation of sulfone compounds

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Nickel-Catalyzed Difunctionalization of Unactivated Alkenes Initiated by Unstabilized Enolates

Cited by 42 publications

References 64 publications

Ni-Catalyzed Regioselective 1,2-Dialkylation of Alkenes Enabled by the Formation of Two C(sp3)–C(sp3) Bonds

Ni-Catalyzed Regioselective 1,2-Dialkylation of Alkenes Enabled by the Formation of Two C(sp3)–C(sp3) Bonds

Nickel‐CatalyzedDicarbofunctionalization of Alkenes†

An efficient transition metal‐free difunctionalization of alkenes in water for the green preparation of sulfone compounds

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Product

Resources

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Ni-Catalyzed Regioselective 1,2-Dialkylation of Alkenes Enabled by the Formation of Two C(sp³)–C(sp³) Bonds

Ni-Catalyzed Regioselective 1,2-Dialkylation of Alkenes Enabled by the Formation of Two C(sp³)–C(sp³) Bonds

Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†