Construction of Polysubstituted Olefins through Ni‐Catalyzed Direct Activation of Alkenyl CO of Substituted Alkenyl Acetates

Sun, Chang‐Liang; Wang, Yang; Xiao, Zhou; Wu, Zhenhua; Li, Bi‐Jie; Guan, Bing‐Tao; Shi, Zhang‐Jie

doi:10.1002/chem.200902785

Cited by 77 publications

(17 citation statements)

References 35 publications

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“…In a particularly elegant demonstration of this chemistry, Garg and co-workers 100 synthesized the anti-inflammatory drug flurbiprofen by directed prefunctionalization of an aryl sulfamate before using the functionalized sulfamate as the electrophile in cross-coupling. Additionally, [(PCy 3 ) 2 NiCl 2 ] can facilitate the Suzuki–Miyaura reaction of alkenyl acetates 108 and α-pivaloxyl ketones 109 , indicating that this precatalyst is compatible with both alkenyl and aryl electrophiles.…”

Section: Ni-based Precatalystsmentioning

confidence: 99%

Well-defined nickel and palladium precatalysts for cross-coupling

2017

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Transition metal-catalysed cross-coupling is one of the most powerful synthetic methods and has led to vast improvements in the synthesis of pharmaceuticals, agrochemicals and precursors for materials chemistry. A major advance in cross-coupling over the past 20 years is the utilization of well-defined, bench-stable Pd and Ni precatalysts that do not require the addition of free ancillary ligand, which can hinder catalysis by occupying open coordination sites on the metal. The development of precatalysts has resulted in new reactions and expanded substrate scopes, enabling transformations under milder conditions and with lower catalyst loadings. This Review highlights recent advances in the development of Pd and Ni precatalysts for cross-coupling, and provides a critical comparison between the state of the art in Pd- and Ni-based systems.

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Section: Ni-based Precatalystsmentioning

confidence: 99%

Well-defined nickel and palladium precatalysts for cross-coupling

2017

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“…Two grams of compound 5ai was obtained in 87% yield from 4a and 2a under the catalysis of 2.5 mol % cobalt at 80 °C. The enol ester 5ai could be transformed into triphenylethene ( 6 ) via a nickel-catalyzed cross-coupling reaction . Ketones 7 and 8 were obtained smoothly under hydrolysis and oxidation conditions, respectively …”

mentioning

confidence: 99%

Enol Ester Synthesis via Cobalt-Catalyzed Regio- and Stereoselective Addition of Carboxylic Acids to Alkynes

Chen

2018

Org. Lett.

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“…While the Ni-catalyzed C–O bond activations 42 , 43 of aryl carbonates 44 , 45 , aryl esters 46 , 47 , and aryl carbamates 48 , 49 are well precedented, the analogous C–O bond activation of vinyl benzoates is less established 50 . Our next goal is to examine the Ni-catalyzed coupling reaction of BzO-DFs with arylboronic acids as nucleophiles through regioselective C(vinyl)–O(benzoate) bond activation.…”

Section: Resultsmentioning

confidence: 99%

2,2-difluorovinyl benzoates for diverse synthesis of gem-difluoroenol ethers by Ni-catalyzed cross-coupling reactions

Chan

Lee

et al. 2021

Nat Commun

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Abstractgem-Difluoroalkene is a bioisostere of carbonyl group for improving bioavailability of drug candidates. Herein we develop structurally diverse 2,2-difluorovinyl benzoates (BzO-DFs) as versatile building blocks for modular synthesis of gem-difluoroenol ethers (44 examples) and gem-difluoroalkenes (2 examples) by Ni-catalyzed cross coupling reactions. Diverse BzO-DFs derivatives bearing sensitive functional groups (e.g., C = C, TMS, strained carbocycles) are readily prepared from their bromodifluoroacetates and bromodifluoroketones precursors using metallic zinc as reductant. With Ni(COD)2 and dppf [1,1’-bis(diphenylphosphino)ferrocene] as catalyst, reactions of BzO-DFs with arylboronic acids and arylmagnesium/alkylzinc reagents afforded the desired gem-difluoroenol ethers and gem-difluoroalkenes in good yields. The Ni-catalyzed coupling reactions features highly regioselective C(vinyl)–O(benzoate) bond activation of the BzO-DFs. Results from control experiments and DFT calculations are consistent with a mechanism involving initial oxidative addition of the BzO-DFs by the Ni(0) complex. By virtue of diversity of the BzO-DFs and excellent functional group tolerance, this method is amenable to late-stage functionalization of multifunctionalized bioactive molecules.

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Construction of Polysubstituted Olefins through Ni‐Catalyzed Direct Activation of Alkenyl CO of Substituted Alkenyl Acetates

Cited by 77 publications

References 35 publications

Well-defined nickel and palladium precatalysts for cross-coupling

Well-defined nickel and palladium precatalysts for cross-coupling

Enol Ester Synthesis via Cobalt-Catalyzed Regio- and Stereoselective Addition of Carboxylic Acids to Alkynes

2,2-difluorovinyl benzoates for diverse synthesis of gem-difluoroenol ethers by Ni-catalyzed cross-coupling reactions

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