Nickel‐Catalyzed Reductive Allylation of Tertiary Alkyl Halides with Allylic Carbonates

Chen, Haifeng; Jia, Xiaodong; Yu, Yinhui; Qian, Qun; Gong, Hegui

doi:10.1002/ange.201705521

Cited by 31 publications

(10 citation statements)

References 58 publications

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“…Allylic carbonates have also been proven to be suitable electrophiles for reductive cross-couplings. [78][79][80] Another nice example of cross-electrophile coupling via nickel/photoredox dual catalysis was described by Chu and co-workers 81 by employing allylic carbonates and vinyl triflates as the substrates (Scheme 8f). In this case, both E-and Z-configured 1,4-dienes could be achieved by the choice of photocatalysts.…”

Section: Nickel-photoredox Dual Catalysismentioning

confidence: 99%

Nickel-Catalyzed Reductive Cross-Couplings: New Opportunities for Carbon–Carbon Bond Formations through Photochemistry and Electrochemistry

et al. 2022

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Metal-catalyzed cross-electrophile couplings have become a valuable tool for carbon-carbon bond formation. This minireview provides a comprehensive overview of the recent developments in the topical field of cross-electrophile couplings, provides explanations of the current state-of-the-art, and highlights new opportunities arising in the emerging fields of photoredox catalysis and electrochemistry.

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Section: Nickel-photoredox Dual Catalysismentioning

confidence: 99%

Nickel-Catalyzed Reductive Cross-Couplings: New Opportunities for Carbon–Carbon Bond Formations through Photochemistry and Electrochemistry

et al. 2022

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“…Two-component allylations, including the Tsuji-Trost reaction [1][2][3][4][5] and crosscoupling with organometallic nucleophiles, [6][7][8][9][10][11][12][13][14][15][16][17][18][19] are well-established and viewed as essential components of the modern synthetic repertoire.…”

Section: Main Textmentioning

confidence: 99%

Integrating Allyl Electrophiles into Nickel-Catalyzed Conjunctive Cross-Coupling

Gallagher

Derosa

et al. 2019

Preprint

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Allylation and conjunctive cross-coupling represent two useful, yet largely distinct, reactivity paradigms in catalysis. The union of these two processes would offer exciting possibilities in organic synthesis but remains largely unknown. Herein, we report the use of allyl electrophiles in nickel-catalyzed conjunctive cross-coupling with a non-conjugated alkene and dimethylzinc. The transformation is enabled by weakly coordinating, monodentate azaheterocycle directing groups, that useful building blocks in synthesis, including saccharin, pyridones, pyrazoles, and triazoles. The reaction occurs under mild conditions and is compatible with a wide range of allyl electrophiles. High chemoselectivity through substrate directivity is demonstrated in the facile reactivity of the β-γ alkene of the starting material, while the ε-ζ alkene of the product is preserved. The generality of this approach is further illustrated through the development of analogous method with alkyne substrates. Mechanistic studies reveal the importance of the weakly coordinating directing group in dissociating to allow binding of the allyl moiety to facilitate C(sp<sup>3</sup>)–C(sp<sup>3</sup>) reductive elimination.

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“…In contrast to the above traditional approaches for the C(sp 3 )–C(sp 3 ) linkages, the nickel or cobalt-catalyzed reductive cross- [14,15,16,17,18,19] and homo-coupling [20,21,22,23] between two alkyl halides have been intensively studied over the past decade (Scheme 1b). In these transformations, a single-electron-transfer (SET) process has been adopted for the initial activation step of alkyl halides, enabling a generation of high-valent dialkyl transition-metal intermediates to lead to C(sp 3 )–C(sp 3 ) linkages via a rapid reductive elimination without a competitive β-H elimination.…”

Section: Introductionmentioning

confidence: 99%

Ni/Co-Catalyzed Homo-Coupling of Alkyl Tosylates

et al. 2019

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A direct reductive homo-coupling of alkyl tosylates has been developed by employing a combination of nickel and nucleophilic cobalt catalysts. A single-electron-transfer-type oxidative addition is a pivotal process in the well-established nickel-catalyzed coupling of alkyl halides. However, the method cannot be applied to the homo-coupling of ubiquitous alkyl tosylates due to the high-lying σ*(C–O) orbital of the tosylates. This paper describes a Ni/Co-catalyzed protocol for the activation of alkyl tosylates on the construction of alkyl dimers under mild conditions.

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Nickel‐Catalyzed Reductive Allylation of Tertiary Alkyl Halides with Allylic Carbonates

Cited by 31 publications

References 58 publications

Nickel-Catalyzed Reductive Cross-Couplings: New Opportunities for Carbon–Carbon Bond Formations through Photochemistry and Electrochemistry

Nickel-Catalyzed Reductive Cross-Couplings: New Opportunities for Carbon–Carbon Bond Formations through Photochemistry and Electrochemistry

Integrating Allyl Electrophiles into Nickel-Catalyzed Conjunctive Cross-Coupling

Ni/Co-Catalyzed Homo-Coupling of Alkyl Tosylates

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