Strategies toward Dicarbofunctionalization of Unactivated Olefins by Combined Heck Carbometalation and Cross-Coupling

Giri, Ramesh; Kc, Shekhar

doi:10.1021/acs.joc.7b03128

Cited by 288 publications

(85 citation statements)

References 81 publications

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“…1, n ‐Difunctionalization ( n >2) products are derived from the catalyst migration to distal positions. These types of reactions are initiated by Heck‐type migratory insertions . Therefore, the stability of the distal position should outcompete the π‐benzyl stabilization acting as the driving force in these reactions.…”

Section: Palladium Catalysismentioning

confidence: 99%

Difunctionalization of Alkenes Involving Metal Migration

Cheng

et al. 2020

Angew Chem Int Ed

268

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The direct difunctionalization of alkenes, a cheap and abundant feedstock, represents one of the most attractive strategies for increasing molecular complexity in synthetic organic chemistry. In contrast with the 1,2‐difunctionalization of alkenes, recent advances showcase alkene 1,n‐difunctionalizations (n≠2) involving metal migration is an emerging and rapidly growing area of research. This promising strategy not only opens a novel avenue for future development of alkene transformations, but also significantly expands upon the bond disconnections available in modern organic synthesis. This Minireview summarizes recent progress in the migratory difunctionalization of alkenes, with an emphasis on the driving force for metal migration.

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Section: Palladium Catalysismentioning

confidence: 99%

Difunctionalization of Alkenes Involving Metal Migration

Cheng

et al. 2020

Angew Chem Int Ed

268

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“…However, the heterodiarylation of alkenes should be more challenging, and the reported reactions have been limited to intramolecular variants or use of special substrates, such as alkenylarenes with a strongly coordinating group, alkenylarenes with an extended conjugation, and so on. Additionally, a major concern of alkene diarylation lies in the potential β‐H elimination and Suzuki–Miyaura cross‐coupling reactions, which are thought to be competitive under the general diarylation conditions …”

Section: Introductionmentioning

confidence: 99%

“…Miyaura cross-coupling reactions, which are thought to be competitive under the general diarylation conditions. [12] Recently, Brown and co-workers [13] reported a nickel-catalyzed heterodiarylation of alkenylarenes (R1), with the use of arylboron reagents (R2) and aryl bromides (R3) as efficient arylating sources (see Scheme 1). The pre-catalyst NiCl 2 and reductant (Bpin) 2 , in the presence of KOEt, were believed to be able to generate a Ni(0) catalyst, which could first undergo oxidative addition of R3 to produce a Ni(II) intermediate.…”

Section: Introductionmentioning

confidence: 99%

A Computational Study on the Reaction Mechanisms of Nickel‐Catalyzed Diarylation of Alkenes

et al. 2019

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A density functional theory study on nickel‐catalyzed diarylation of styrene (R1) with arylboron (R2) and aryl bromide (R3) is presented in this article, to unveil the plausible mechanism and the competition of the potential side reactions. The located reaction pathway involves the elementary steps of oxidative addition, migratory insertion, transmetalation, and reductive elimination. The total free‐energy barrier is computed to be 27.3 kcal/mol, which should be consistent with the experimental temperature and reaction time reported. The Heck coupling reactions between R1 and R3 in the absence and presence of R2 are investigated at the same level of theory, respectively, and it is found that the presence of R2 could not only favor the formation of a η3‐benzyl‐Ni complex leading to the desired diarylation but also disfavor the undesired β‐H elimination step as well. The Suzuki–Miyaura coupling pathway is also suppressed under the optimal conditions, because the migratory insertion of R1 takes place prior to the transmetalation of R2. However, addition of a strongly coordinating ligand could hinder the entry of R1 into the ligand field, which may retard the diarylation pathway and make the cross‐coupling pathway dominant.

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“…T ransition-metal-catalyzed dicarbofunctionalization consisting of a cyclization/cross-coupling cascade provides a powerful method to access various benzene-fused cyclic compounds starting from tethered alkenes [1][2][3][4][5][6][7][8][9][10][11][12][13] . Both redoxneutral [2][3][4][5][6][7] and reductive [8][9][10][11][12][13] strategies have been successfully applied in this reaction.…”

mentioning

confidence: 99%

Nickel-catalyzed enantioselective reductive carbo-acylation of alkenes

Lan

Wang

2020

Commun Chem

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Recently, transition-metal-catalyzed asymmetric dicarbofunctionalization of tethered alkenes has emerged as a powerful method for construction of chiral cyclic carbo-and heterocycles. However, all these reactions rely on facially selective arylmetalation of the pendant olefinic unit. Here, we successfully apply acylnickelation as the enantiodetermining step in the asymmetric nickel-catalyzed reductive carbo-acylation of aryl carbamic chloride-tethered alkenes with primary and secondary alkyl iodides as well as benzyl chlorides as the coupling partners, using manganese as a reducing agent. By circumventing the use of pre-generated organometallics, this reductive strategy enables the synthesis of diverse enantioenriched oxindoles bearing a quaternary stereogenic center under mild reaction conditions with high tolerance of a broad range of functional moieties.

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Strategies toward Dicarbofunctionalization of Unactivated Olefins by Combined Heck Carbometalation and Cross-Coupling

Cited by 288 publications

References 81 publications

Difunctionalization of Alkenes Involving Metal Migration

Difunctionalization of Alkenes Involving Metal Migration

A Computational Study on the Reaction Mechanisms of Nickel‐Catalyzed Diarylation of Alkenes

Nickel-catalyzed enantioselective reductive carbo-acylation of alkenes

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