Selected Patented Cross-Coupling Reaction Technologies

Corbet, Jean‐Pierre; Mignani, Gérard

doi:10.1021/cr0505268

Cited by 1,725 publications

(600 citation statements)

References 281 publications

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“…Halogen-containing substrates (1 e) can also be tolerated, affording the possibility for further transformations. [47] Different functionalities on the phenyl ring of the leaving group were also tested. Neither electron-rich nor electrondeficient leaving groups (1 i and 1 j) affected the efficiency dramatically.…”

Section: Resultsmentioning

confidence: 99%

Rh‐Catalyzed CC Cleavage of Benzyl/Allylic Alcohols to Produce Benzyl/Allylic Amines or other Alcohols by Nucleophilic Addition of Intermediate Rhodacycles to Aldehydes and Imines

Zhang¹,

Li²,

Li³

et al. 2012

Chemistry A European J

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We report three transformations: 1) direct transformation from biarylmethanols into biarylmethylamines; 2) direct transformation from one biarylmethanol into another biarylmethanol; 3) direct transformation from allylic alcohols into allylic amines. These transformations are based on pyridyl‐directed Rh‐catalyzed CC bond cleavage of secondary alcohols and subsequent addition to CX (X=N or O) double bonds. The reaction conditions are simple and no additive is required. The driving force of CC bond cleavage is the formation of the stable rhodacycle intermediate. Other directing groups, such as the pyrazolyl group, can also be used although it is not as efficient as the pyridyl group. We carried out in‐depth investigations for transformation 1 and found that: 1) the substrate scope was broad and electron‐rich alcohols and electron‐deficient imines are more efficient; 2) as the leaving group, aldehyde had no significant impact on either the CC bond cleavage or the whole transformation; 3) mechanistic studies (intermediate isolation, in situ NMR spectroscopic studies, competing reactions, isotopic labeling experiments) implied that: i) The CC cleavage was very efficient under these conditions; ii) there is an equilibrium between the rhodacycle intermediate and the protonated byproduct phenylpyridine; iii) the addition step of the rhodacycle intermediate to imines was slower than the CC cleavage and the equilibrium between the rhodacycle and phenylpyridine; iv) the whole transformation was a combination of two sequences of CC cleavage/nucleophilic addition and CC cleavage/protonation/CH activation/nucleophilic addition, with the latter being perhaps the main pathway. We also demonstrated the first example of cleavage of an C(alkenyl)C(benzyl) bond. These transformations showed the exchange (or substitution) of the alcohol group with either an amine or another alcohol group. Like the “group transplant”, this method offers a new concept that can be used to directly synthesize the desired products from other chemicals through reorganization of carbon skeletons.

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Section: Resultsmentioning

confidence: 99%

Rh‐Catalyzed CC Cleavage of Benzyl/Allylic Alcohols to Produce Benzyl/Allylic Amines or other Alcohols by Nucleophilic Addition of Intermediate Rhodacycles to Aldehydes and Imines

Zhang¹,

Li²,

Li³

et al. 2012

Chemistry A European J

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“…because of their ability to construct carbon-carbon bonds [169,170]. In 2010, Richard Heck, Ei-ichi Negishi, and Akira Suzuki jointly received the Nobel Prize for Chemistry for their roles in discovering and developing highly practical method for palladium-catalyzed cross-coupling reactions [171][172][173].…”

Section: C-c Coupling Reactionsmentioning

confidence: 99%

Graphitized nanocarbon-supported metal catalysts: synthesis, properties, and applications in heterogeneous catalysis

Huang

2017

Sci. China Mater.

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Graphitized nanocarbon materials can be an ideal catalyst support for heterogeneous catalytic systems. Their unique physical and chemical properties, such as large surface area, high adsorption capacity, excellent thermal and mechanical stability, outstanding electronic properties, and tunable porosity, allow the anchoring and dispersion of the active metals. Therefore, currently they are used as the key support material in many catalytic processes. This review summarizes recent relevant applications in supported catalysts that use graphitized nanocarbon as supports for catalytic oxidation, hydrogenation, dehydrogenation, and C-C coupling reactions in liquid-phase and gas-solid phase-reaction systems. The latest developments in specific features derived from the morphology and characteristics of graphitized nanocarbon-supported metal catalysts are highlighted, as well as the differences in the catalytic behavior of graphitized nanocarbon-supported metal catalysts versus other related catalysts. The scientific challenges and opportunities in this field are also discussed. Keywords: nanocarbon materials; graphitized carbon supports; metal catalysts; hetergeneous catalysis INTRODUCTIONCarbon combines its atoms in diverse hybridization states (sp, sp 2 , sp 3 ) to form a variety of polymorphs. These are composed entirely of carbon but have different physical structures and different names, including diamond, graphite, fullerenes, and carbines, among others [1][2][3][4][5]. Because these various and versatile allotropes produce materials with a large range of properties, carbon materials can be used in a number of technological processes, including high-tech catalytic ones [6][7][8][9][10].In heterogeneous catalysis, carbon material plays wellestablished and important roles in a wide range of applications, both as catalyst in its own right and as a unique support material [11][12][13][14][15]. The chemical stability of carbon supports in some specifically aqueous phase biomass conversion surpasses that of metal oxide materials; in addition, carbon materials present other common and key advantages as support materials for catalysis [1,5]. From the point of physical structure, porous carbon can be prepared in different forms (granules, cloth, fibers, pallets, etc.). Due to its chemical properties, carbon structure is resistant to both acidic and basic media. The structure of carbon is stable at high temperature (even above 1023 K under inert atmosphere). The hydrophilic/ hydrophobic nature of carbon can be easily modified. Active metals on the support can be easily reduced. For the purposes of industrial economy and environment, the active phase can be easily recovered. Conventional carbon supports are lower-cost and more easily available than other conventional supports. Although several kinds of carbon materials have been studied, active carbon (AC) [12,[16][17][18][19] and, to a lesser extend, carbon black [20][21][22][23] have long been the most commonly used carbon supports. AC is an amorphous solid prepa...

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“…Além disso, complexos de níquel são tóxicos e há necessidade do tratamento de resíduos com elevadas quantidades de magnésio. 24 O acoplamento de Kumada pode ser aplicado a processos em escala industrial, além de ser realizado sob condições reacionais brandas. Embora complexos de níquel sejam tóxicos, a possibilidade de empregá-los é bastante interessante devido ao menor preço deste metal em relação ao paládio.…”

Section: Esquema 2 Metodologia De Kharasch E Fields Para Obtenção Deunclassified

Kumada-Corriu-Tamao couplings catalyzed by Ni and Pd as an important tool for the biaryl synthesis

Martins¹

2010

Revista Virtual De Química

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Abstract:Cross-coupling reactions catalyzed by transition metal complexes are important tools in the synthesis of biaryls, building blocks in a variety of compounds with interesting applications. The contributions of the palladium-catalyzed cross-coupling reactions to organic synthesis were recognized in 2010 when R. F. Heck, E. Negishi and A. Suzuki were awarded the Nobel Prize in Chemistry. Biarylic systems are usually obtained by a C(sp 2 )-C(sp 2 ) bond formation process catalyzed by Ni or Pd and several methodologies are currently available for their synthesis, for example, the Suzuki reaction, or Stille, Hiyama, Negishi, or Kumada-Corriu-Tamao crosscoupling. In this work, the Kumada-Corriu-Tamao methodology is investigated. The main characteristics of the reaction, like the catalytic systems employed, the different classes of substrates, and the optimization of the experimental protocol will be discussed as well. Application of this methodology in the synthesis of molecules of interest will also be addressed. The Kumada-Corriu-Tamao methodology is claimed to be the precursor of all other cross-coupling methodologies, pushing the frontiers of the organic synthesis.Keywords: biaryls; C-C coupling; Kumada-Corriu-Tamao; niquel; palladium; Nobel 2010. ResumoOs acoplamentos cruzados catalisados por metais de transição são ferramentas muito importantes na construção de sistemas biarílicos, os quais estão presentes na estrutura de diversas substâncias com aplicações importantes na terapêutica médica e na indústria química. A importância dos acoplamentos cruzados foi reconhecida pela concessão do prêmio Nobel de 2010 aos pesquisadores R. F. Heck, E. Negishi e A. Suzuki. Geralmente, os sistemas biarílicos são obtidos mediante a formação de ligações C(sp 2 )-C(sp 2 ) entre dois anéis aromáticos através de um processo catalisado por Ni ou Pd. Várias metodologias de acoplamento estão disponíveis para o preparo de biarilas como, por exemplo, as reações de Suzuki, Stille, Hiyama, Negishi ou Kumada-Corriu-Tamao. Neste trabalho, será abordado o acoplamento de Kumada-Corriu-Tamao: as características principais, os sistemas catalíticos empregados, os diferentes substratos e o processo de desenvolvimento da metodologia que alavancou os acoplamentos cruzados conhecidos e largamente empregados atualmente.

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Selected Patented Cross-Coupling Reaction Technologies

Cited by 1,725 publications

References 281 publications

Rh‐Catalyzed CC Cleavage of Benzyl/Allylic Alcohols to Produce Benzyl/Allylic Amines or other Alcohols by Nucleophilic Addition of Intermediate Rhodacycles to Aldehydes and Imines

Rh‐Catalyzed CC Cleavage of Benzyl/Allylic Alcohols to Produce Benzyl/Allylic Amines or other Alcohols by Nucleophilic Addition of Intermediate Rhodacycles to Aldehydes and Imines

Graphitized nanocarbon-supported metal catalysts: synthesis, properties, and applications in heterogeneous catalysis

Kumada-Corriu-Tamao couplings catalyzed by Ni and Pd as an important tool for the biaryl synthesis

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