Carbon−Carbon Formation via Ni-Catalyzed Suzuki−Miyaura Coupling through C−CN Bond Cleavage of Aryl Nitrile

Yu, Da‐Gang; Yu, Miao; Guan, Bing‐Tao; Li, Bi‐Jie; Yang, Zheng; Wu, Zhenhua; Shi, Zhang‐Jie

doi:10.1021/ol901217m

Cited by 117 publications

(69 citation statements)

References 47 publications

(11 reference statements)

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“…The latter result can be explained by competitive cross-coupling at the cyano group, a transformation reported recently by Shi. 24 Finally, an electron-rich substrate gave only low yields of product (entry 6).…”

Section: Resultsmentioning

confidence: 99%

Suzuki−Miyaura Cross-Coupling of Aryl Carbamates and Sulfamates: Experimental and Computational Studies

et al. 2011

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The first Suzuki–Miyaura cross-coupling reactions of the synthetically versatile O-aryl carbamate and O-sulfamate groups is described. The transformations utilize the inexpensive, bench-stable catalyst NiCl2(PCy3)2 to furnish biaryls in good to excellent yields. A broad scope for this methodology has been demonstrated. Substrates with electron-donating and electron-withdrawing groups (EDGs, EWGs) are tolerated, in addition to those that possess ortho substitutents. Furthermore, heteroaryl substrates may be employed as coupling partners. A computational study providing the full catalytic cycles for these cross-coupling reactions is described. The oxidative additions with carbamates and sulfamates occur via a five-centered transition state, resulting in the exclusive cleavage of the Ar–O bond. Water is found to stabilize the Ni–carbamate catalyst resting state, and thus provides rationalization of the relative decreased rate of coupling of carbamates. Several synthetic applications are presented to showcase the utility of the methodology in the synthesis of polysubstituted aromatic compounds of natural product and bioactive molecule interest.

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Section: Resultsmentioning

confidence: 99%

Suzuki−Miyaura Cross-Coupling of Aryl Carbamates and Sulfamates: Experimental and Computational Studies

et al. 2011

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“…Along with traditional aryl halides, it can also couple heteroaryl halides 99 , as well as aryl mesylates 99 , carbamates 99–103 , carbonates 100 , sulfamates 99,101 , phosphates 104 , nitriles 105 , twisted amides 106 and pivalates 99,100,107 with boronic acids, boroxines or mixtures of both nucleophiles. 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.…”

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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“…Some representative electrophiles include aryl tellurides 87 [49], aryldiazonium tetrafluoroborates 88 [50], aryltrimethylammonium salts 89 [51], aryltriazenes 90 [52], arylsulfonyl chlorides 91 [53], and arylcyanides 92 (Scheme 2.15) [54]. While these pseudohalides exhibit interesting cross-coupling reactivity, their availability remains limited.…”

Section: Pseudohalidesmentioning

confidence: 99%

State‐of‐the‐Art in Metal‐Catalyzed Cross‐Coupling Reactions of Organoboron Compounds with Organic Electrophiles

Lee

Hall

2013

Metal‐Catalyzed Cross‐Coupling Reactions and More

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Carbon−Carbon Formation via Ni-Catalyzed Suzuki−Miyaura Coupling through C−CN Bond Cleavage of Aryl Nitrile

Abstract: The Suzuki-Miyaura coupling of aryl nitriles with aryl/alkenyl boronic esters is reported. With this method, the cyano group could be applied as a protecting group of arenes and finally as a leaving group to further construct polyaryl scaffolds.

Cited by 117 publications

References 47 publications

Suzuki−Miyaura Cross-Coupling of Aryl Carbamates and Sulfamates: Experimental and Computational Studies

Suzuki−Miyaura Cross-Coupling of Aryl Carbamates and Sulfamates: Experimental and Computational Studies

Well-defined nickel and palladium precatalysts for cross-coupling

State‐of‐the‐Art in Metal‐Catalyzed Cross‐Coupling Reactions of Organoboron Compounds with Organic Electrophiles

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