Progress in Difunctionalization of Alkenes

Fu, Xiao-Fei; Zhao, Wen

doi:10.6023/cjoc201808031

Cited by 40 publications

(32 citation statements)

References 11 publications

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“…[ 1‐7 ] Among the developed methods, transition metal‐catalyzed difunctionalization of alkenes enables preparation of complex molecules from simple available alkenes by diversifying the C=C double bond with high atom‐ and step‐economic efficiency. [ 8‐21 ] In particular, the dicarbofunctionalization of alkenes has gained special attention because it can construct complex carbon skeletons by assembling two carbon entities across the C=C bond and forming two C—C bonds in an one‐pot reaction (Scheme 1). [ 22‐25 ] Over the past decade, considerable efforts have been devoted to this area and impressive progress has been achieved.…”

Section: Introductionmentioning

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: Introductionmentioning

confidence: 99%

Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†

2020

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“…73-75 °C, R f = 0.32 (PE/EtOAc 10 : 1, v/v). 1 H NMR (400 MHz, CDCl 3 ) δ 7.96 (d, J = 8.4 Hz, 2H, ArH), 7.56-7.49 (m, 2H, ArH), 7.49-7.44 (m, 1H, ArH), 7.41-7.32 (m, 4H, ArH), 2.47 (s, 3H). 13 C NMR (101 MHz, CDCl 3 ) δ 145.4, 138.9, 132.7, 131.4, 130.0, 128.6, 127.5, 118.0, 93.0, 85.6, 21.7.…”

Section: Methodsmentioning

confidence: 99%

“…73-75 °C, R f = 0.25 (PE/EtOAc 10 : 1, v/v). 1 H NMR (400 MHz, CDCl 3 ) δ 8.13-8.05 (m, 2H, ArH), 7.74-7.65 (m, 1H, ArH), 7.62-7.56 (m, 2H, ArH), 7.42 (d, J = 8.2 Hz, 2H, ArH), 7.18 (d, J = 7.9 Hz, 2H, ArH), 2.37 (s, 3H). 13 C NMR (101 MHz, CDCl 3 ) δ 142.4, 142.0, 134.0, 132.7, 129.5, 129.3, 127.3, 114.7, 94.2, 84.9, 21.8.…”

Section: -Fluoro-3-((phenylsulfonyl)ethynyl)benzene (1 D)mentioning

confidence: 99%

“…91-92 °C, R f = 0.30 (PE/EtOAc 10 : 1, v/v). 1 H NMR (400 MHz, CDCl 3 ) δ 7.95 (d, J = 8.0 Hz, 2H, ArH), 7.76-7.70 (m, 1H, ArH), 7.39 (d, J = 8.2 Hz, 2H, ArH), 7.33-7.30 (m, 1H, ArH), 7.20-7.12 (m, 1H, ArH), 2.47 (s, 3H). 13 [26] White solid, yield: 191 mg, 43%; M.p.…”

Section: -(Tosylethynyl)benzo[d][13]dioxole (1 O)mentioning

confidence: 99%

“…58-59 °C, R f = 0.25 (PE/EtOAc 3 : 1, v/v). 1 H NMR (400 MHz, CDCl 3 ) δ 7.59-7.43 (m, 5H, ArH), 3.31 (s, 3H). 13 C NMR (101 MHz, CDCl 3 ) δ 132.8, 131.7, 128.8, 117.5, 91.5, 84.4, 46.8.…”

Section: -Methyl-4-(pent-1-yn-1-ylsulfonyl)benzene (1 S)mentioning

confidence: 99%

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Direct 1,2‐Oxosulfenylation of Acetylenic Sulfones with DMSO

Dong

Wang

et al. 2021

Asian J Org Chem

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Direct 1,2-oxosulfenylation of acetylenic sulfones with dimethyl sulfoxide (DMSO) is realized under microwave irradiation. The current method provides a direct and efficient route to synthesize β-keto thiosulfones from acetylenic sulfones and DMSO, featuring metal-free, low cost, and convenient advantages. The mechanistic investigations in-dicate that acetylenic sulfones first react with DMSO to generate sulfonium ylides through the nucleophilic addition, cyclization, and 4e ring opening. The sulfonium ylides and the DMSO-generated dimethyl sulfide at the aid of the ylides undergo a radical process to form β-keto thiosulfones under heating.

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