Nickel-Catalyzed Intramolecular Arylcyanation for the Synthesis of 3,3-Disubstituted Oxindoles

Yen, Andy; Lautens, Mark

doi:10.1021/acs.orglett.8b01772

Cited by 34 publications

(13 citation statements)

References 69 publications

(40 reference statements)

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“…They developed a nickel‐catalyzed arylcyanation for the synthesis of 3,3‐disubstituted oxindoles (Scheme 59). [ 129 ] A variety of heterocycles exhibited good tolerance to the reaction, providing an efficient route for applications in organic synthesis.…”

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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Section: Intramolecular Dicarbofunctionalization Of Alkenes Via Cyclimentioning

confidence: 99%

Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†

2020

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“…Our group and others have extensively investigated the intramolecular 1,2-carbofunctionalization of olefins . Utilizing this approach, Fagnou, Zhu, and Sharma and Van der Eycken have reported trapping of the σ-Pd intermediate with activated heterocycles (Scheme a).…”

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Palladium-Catalyzed Arylation/Heteroarylation of Indoles: Access to 2,3-Functionalized Indolines

et al. 2018

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“…35 We reported that a NiCl 2 (glyme)−DIOP catalytic system furnished cyanated oxindole products with the use of Zn(CN) 2 as the source of cyanide (Scheme 12). 36 The inclusion of activated zinc dust in the reaction mixture avoided the use of airsensitive Ni(COD) 2 , enabling the use of an easily handled NiCl 2 (glyme) precatalyst. In one substrate we observed an example of a nickel-catalyzed "chain walking" reaction, pioneered by the works of Martin and Marek, and others, 37 that generated a remotely cyanated oxindole scaffold.…”

Section: Anion-capture Cascade Reactionsmentioning

confidence: 99%

Metal-Catalyzed Approaches toward the Oxindole Core

et al. 2020

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Conspectus The oxindole scaffold is a privileged structural motif that is found in a variety of bioactive targets and natural products. Moreover, derivatives of the oxindole structure are widely present in a number of biologically relevant compounds and are key intermediates in the synthesis of diverse natural products and pharmaceuticals. Therefore, novel methods to obtain oxindoles remain of high priority in synthetic organic chemistry. Over the past several decades, novel transition-metal-catalyzed methodologies have been applied toward the synthesis of a variety of heterocycles. A detailed mechanistic understanding facilitates the disruption of traditional catalytic pathways to access useful synthetic intermediates. The strategies employed have generally revolved around the generation of high-energy organometallic intermediates, which undergo cyclization reactions through domino processes. Domino cyclization methodologies are therefore attractive, as they allow facile access to functionalized oxindoles containing all-carbon quaternary centers or tetrasubstituted olefins with high chemo- and stereoselectivities. Furthermore, these developed synthetic strategies can often be easily applied in the syntheses of other related scaffolds. In this Account, we discuss the three unique strategies that our group has leveraged for the synthesis of valuable oxindole scaffolds. The first section in this Account outlines the use of an initial oxidative addition to a C(sp2)–X bond, followed by a migratory insertion, yielding a neopentyl species amenable to a variety of subsequent functionalizations. From this reactive neopentyl metal species, we have reported C–X reductive eliminations, anionic capture cascade reactions, and intramolecular C–H functionalization processes. The second section of this Account summarizes our group’s findings on 1,2-insertions of a metal–nucleophile species across an unsaturation, generating a reactive organometallic intermediate; subsequent reactions with tethered electrophiles form the desired heterocyclic core. We have explored a wide array of transition metal-catalyzed strategies using this approach, including rhodium-catalyzed conjugate additions, an asymmetric copper-catalyzed borylcupration, and a palladium(II)-catalyzed chloropalladation protocol. The final section of this Account details the use of dual-metal catalysis to perform a cyclization through a C–H functionalization–allylation domino reaction. Throughout this Account, we provide details of mechanistic studies that better enabled our understanding of the domino processes. Overall, our group has developed methods exploiting the unique reactivity of palladium, nickel, copper, rhodium, and ruthenium catalysts to develop methods toward a wide array of oxindole scaffolds. On the basis of the utility, diversity, and applicability of the strategies developed, we believe that they will prove to be highly useful in the syntheses of other important targets and inspire further development and mechanistic understanding of various metal-c...

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Nickel-Catalyzed Intramolecular Arylcyanation for the Synthesis of 3,3-Disubstituted Oxindoles

Cited by 34 publications

References 69 publications

Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†

Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†

Palladium-Catalyzed Arylation/Heteroarylation of Indoles: Access to 2,3-Functionalized Indolines

Metal-Catalyzed Approaches toward the Oxindole Core

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Nickel-Catalyzed Intramolecular Arylcyanation for the Synthesis of 3,3-Disubstituted Oxindoles

Cited by 34 publications

References 69 publications

Nickel‐CatalyzedDicarbofunctionalization of Alkenes†

Nickel‐CatalyzedDicarbofunctionalization of Alkenes†

Palladium-Catalyzed Arylation/Heteroarylation of Indoles: Access to 2,3-Functionalized Indolines

Metal-Catalyzed Approaches toward the Oxindole Core

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Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†

Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†