Nickel/Lewis Acid-Catalyzed Carbocyanation of Unsaturated Compounds

Nakao, Yoshiaki

doi:10.1246/bcsj.20120081

Cited by 75 publications

(17 citation statements)

References 157 publications

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“…Recently, N ‐cyano‐ N ‐phenyl‐ p ‐toluene sulfonamide (NCTS) has been employed as a bench‐stable and less‐toxic cyanation reagent in metal‐catalyzed cross‐coupling21 and arene CH cyanations,22 thus implying a metal‐mediated NCN cleavage process. Meanwhile, Lewis acid cocatalysts, particularly BPh 3 , have proven effective at accelerating metal‐catalyzed carbocyanation23 and oxycyanation10 of alkenes.…”

Section: Methodsmentioning

confidence: 99%

Intramolecular Aminocyanation of Alkenes by NCN Bond Cleavage

et al. 2014

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A metal-free, Lewis acid promoted intramolecular aminocyanation of alkenes was developed. B(C 6 F 5 ) 3 activates N-sulfonyl cyanamides, thus leading to a formal cleavage of the NÀCN bonds in conjunction with vicinal addition of sulfonamide and nitrile groups across an alkene. This method enables atom-economical access to indolines and tetrahydroquinolines in excellent yields, and provides a complementary strategy for regioselective alkene difunctionalizations with sulfonamide and nitrile groups. Labeling experiments with 13 C suggest a fully intramolecular cyclization pattern due to the lack of label scrambling in double crossover experiments. Catalysis with Lewis acid is realized and the reaction can be conducted under air.

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Section: Methodsmentioning

confidence: 99%

Intramolecular Aminocyanation of Alkenes by NCN Bond Cleavage

et al. 2014

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“…[ 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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“…[1][2][3][4] Most notably, Nakao and Hiyama have disclosed a Nicatalyzed alkyne insertion reaction into CÀ CN bonds that can be used for the atom-economical synthesis of vinyl nitriles. [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21] Inspired by this unique reactivity, our group has developed a host of transformations that rely on the reversibility of the CÀ CN oxidative addition step. [22 -27] This includes both nickel-catalyzed transfer hydrocyanation and aryl cyanation reactions that elude the need for toxic cyanide-based reagents such as HCN or KCN.…”

Section: Introductionmentioning

confidence: 99%