How Rhodium(I)-Catalyzed Phosphorus(III)-Directed C–H Bond Functionalizations Can Improve the Catalytic Activities of Phosphines

Synlett ◽  
2022 ◽  
Author(s):  
Jean-François Soulé ◽  
Zhuan Zhang ◽  
Natacha Durand
Keyword(s):  
Late Stage ◽  
Bond Activation ◽  
Materials Science ◽  
Phosphine Ligands ◽  
Coupling Reactions ◽  
Catalytic Activities ◽  
Cross Coupling Reactions ◽  
Phosphorus Containing ◽  
Directing Group ◽  
Metal Catalyzed

AbstractTrivalent-phosphorus-containing molecules are widely used in fields ranging from catalysis to materials science. Efficient catalytic methods for their modifications, providing straightforward access to novel hybrid structures with superior catalytic activities, are highly desired to facilitate reaction improvement or discovery. We have recently developed new methods for synthesizing polyfunctional phosphines by C–C cross-couplings through rhodium-catalyzed C–H bond activation. These methods use a native P(III) atom as a directing group, and can be used in regioselective late-stage functionalization of phosphine ligands. Interestingly, some of the modified phosphines outperform their parents in Pd-catalyzed cross-coupling reactions.1 Introduction2 Early Examples of Transition-Metal-Catalyzed P(III)-Directed C–H Bond Activation/Functionalizations3 Synthesis of Polyfunctional Biarylphosphines by Late-Stage Alkylation: Application in Carboxylation Reactions4 Synthesis of Polyfunctional Biarylphosphines by Late-Stage Alkenylation: Application in Amidation Reactions5 Conclusion

scholarly journals Rapid Access to Diverse Potassium Acyltrifluoroborates (KATs) Through Late-Stage Chemoselective Cross-Coupling Reactions

2020 ◽  
Author(s):  
Xingwang Deng ◽  
Guan Zhou ◽  
Xiao Han ◽  
Khadim Ullah ◽  
Rajavel Srinivasan
Keyword(s):  
Late Stage ◽  
Materials Science ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Library Synthesis ◽  
Reaction Conditions ◽  
Cross Coupling Reactions ◽  
Rapid Diversification ◽  
High Yields ◽  
Opening Up

Potassium acyltrifluoroborates (KATs) are opening up new avenues in chemical biology, materials science and synthetic organic chemistry due to their intriguing reactivities. However, the synthesis of these compounds remains mostly complicated and time-consuming. This lack of a rapid and facile synthetic route has hindered the widespread adoption of KAT-based chemistry, especially in the areas of compound library synthesis and drug discovery. Herein, we have developed chemoselective Pd-catalyzed approaches for the late-stage diversification of arenes bearing pre-functionalized KATs. These approaches feature chemoselective cross-coupling, rapid diversification, functional group tolerance, mild reaction conditions, and high yields.

scholarly journals Photo-Induced Thiolate Catalytic Activation of Inert Caryl-Hetero Bonds for Radical Borylation

2020 ◽  
Author(s):  
Shun Wang ◽  
Hua Wang ◽  
Burkhard Koenig
Keyword(s):  
Bond Activation ◽  
Reducing Power ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Reaction Conditions ◽  
Catalytic Activation ◽  
Cross Coupling Reactions ◽  
Recent Developments ◽  
Leaving Groups ◽  
Metal Catalyzed

Cross-coupling reactions are essential tools in modern synthesis of drugs, natural products and materials. The recent developments in photocatalytic radical generation have improved and expanded the classic metal-catalyzed cross coupling reactions even further. However, for sp<sup>2</sup> cross coupling reactions aryl halides or related active leaving groups, such as triflates, are required. Substituted arenes bearing strong C-X bonds remain inert to current methods. We describe now a new thiolate photocatalysis for the activation of inert substituted arenes in ipso-borylation reactions. This catalytic system exhibits strong reducing power and allows the borylation of stable C<sub>aryl</sub>−F, C<sub>aryl</sub>−O, C<sub>aryl</sub>-N and C<sub>aryl</sub>−S bonds, which are considered as chemically stable at mild reaction conditions. Our method considerably widens the available substrate scope of aryl radical precursors and we anticipate that this report will inspire new chemistry based on inert chemical bond activation.

scholarly journals Rapid Access to Diverse Potassium Acyltrifluoroborates (KATs) Through Late-Stage Chemoselective Cross-Coupling Reactions

2020 ◽  
Author(s):  
Xingwang Deng ◽  
Guan Zhou ◽  
Xiao Han ◽  
Khadim Ullah ◽  
Rajavel Srinivasan
Keyword(s):  
Late Stage ◽  
Materials Science ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Library Synthesis ◽  
Reaction Conditions ◽  
Cross Coupling Reactions ◽  
Rapid Diversification ◽  
High Yields ◽  
Opening Up

Potassium acyltrifluoroborates (KATs) are opening up new avenues in chemical biology, materials science and synthetic organic chemistry due to their intriguing reactivities. However, the synthesis of these compounds remains mostly complicated and time-consuming. This lack of a rapid and facile synthetic route has hindered the widespread adoption of KAT-based chemistry, especially in the areas of compound library synthesis and drug discovery. Herein, we have developed chemoselective Pd-catalyzed approaches for the late-stage diversification of arenes bearing pre-functionalized KATs. These approaches feature chemoselective cross-coupling, rapid diversification, functional group tolerance, mild reaction conditions, and high yields.

Air-stable phosphine oxides as preligands for catalytic activation reactions of C-Cl, C-F, and C-H bonds

2006 ◽  
Vol 78 (2) ◽  
pp. 209-214 ◽  
Author(s):  
Lutz Ackermann ◽  
Robert Born ◽  
Julia H. Spatz ◽  
Andreas Althammer ◽  
Christian J. Gschrei
Keyword(s):  
Bond Activation ◽  
Bond Formation ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Phosphine Oxides ◽  
Aryl Chlorides ◽  
Catalytic Activation ◽  
Cross Coupling Reactions ◽  
Palladium Catalyzed ◽  
Metal Catalyzed

Studies on the use of easily accessible heteroatom-substituted secondary phosphine oxides as preligands for cross-coupling reactions are described. These air-stable sterically hindered phosphine oxides allow for efficient palladium-catalyzed Suzuki- and nickel-catalyzed Kumada-coupling reactions using electronically deactivated aryl chlorides. In addition, they enable nickel-catalyzed coupling reactions of magnesium organyls with aryl fluorides at ambient temperature, and ruthenium-catalyzed coupling reactions of aryl chlorides via C-H bond activation. Finally, the application of modular diamino phosphine chlorides as preligands for a variety of transition-metal-catalyzed C-C and C-N bond formation reactions employing electron-rich aryl chlorides is presented.

scholarly journals Photo-Induced Thiolate Catalytic Activation of Inert Caryl-Hetero Bonds for Radical Borylation

2020 ◽  
Author(s):  
Shun Wang ◽  
Hua Wang ◽  
Burkhard Koenig
Keyword(s):  
Bond Activation ◽  
Reducing Power ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Reaction Conditions ◽  
Catalytic Activation ◽  
Cross Coupling Reactions ◽  
Recent Developments ◽  
Leaving Groups ◽  
Metal Catalyzed

Cross-coupling reactions are essential tools in modern synthesis of drugs, natural products and materials. The recent developments in photocatalytic radical generation have improved and expanded the classic metal-catalyzed cross coupling reactions even further. However, for sp<sup>2</sup> cross coupling reactions aryl halides or related active leaving groups, such as triflates, are required. Substituted arenes bearing strong C-X bonds remain inert to current methods. We describe now a new thiolate photocatalysis for the activation of inert substituted arenes in ipso-borylation reactions. This catalytic system exhibits strong reducing power and allows the borylation of stable C<sub>aryl</sub>−F, C<sub>aryl</sub>−O, C<sub>aryl</sub>-N and C<sub>aryl</sub>−S bonds, which are considered as chemically stable at mild reaction conditions. Our method considerably widens the available substrate scope of aryl radical precursors and we anticipate that this report will inspire new chemistry based on inert chemical bond activation.

scholarly journals Nickel-Catalyzed Ipso-Borylation of Silyloxyarenes via C–O Bond Activation

2021 ◽  
Author(s):  
Wesley Pein ◽  
Eric Wiensch ◽  
John Montgomery
Keyword(s):  
Bond Activation ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Nickel Catalysis ◽  
Silyl Ethers ◽  
Cross Coupling Reactions ◽  
Boronic Esters ◽  
Directing Group ◽  
Aromatic Systems ◽  
Oxygen Bond

A mild method to convert silyloxyarenes to pinacol boronic esters using nickel catalysis is described. In contrast to other borylation protocols of relatively inert C–O bonds, the method is competent in activating the carbon-oxygen bond of silyloxyarenes in isolated aromatic systems lacking a directing group. The catalytic functionalization of benzyl silyl ethers was also achieved under these conditions. Orthogonal reactivity of silyloxyarenes vs other electrophiles was demonstrated in the case of several cross-coupling reactions wherein the unaffected silyloxarene could be functionalized subsequently.

Recent Advances in Microwave Promoted C-P Cross-coupling Reactions

2020 ◽  
Vol 7 (2) ◽  
pp. 112-122
Author(s):  
Sujit Ghosh ◽  
Kinkar Biswas ◽  
Basudeb Basu
Keyword(s):  
Phosphinic Acid ◽  
Cross Coupling ◽  
Phosphine Ligands ◽  
Water Soluble ◽  
Conventional Heating ◽  
Microwave Assisted Synthesis ◽  
Coupling Reactions ◽  
Cross Coupling Reactions ◽  
Organophosphorous Compounds ◽  
Metal Catalyzed

: Organophosphorous compounds are of potential importance in diverse fields. They are often used as intermediates for making functionalized phosphine ligands as well as find vast applications in the areas of industrial, agricultural and biological chemistry. The microwave-assisted synthesis of C-P bonds has become increasingly popular because of its various advantages over conventional heating in the perspectives of green chemistry. : This review article has primarily focused on the synthesis of various organophosphorous molecules via microwave promoted C-P cross-coupling reactions under metal-catalyzed or metal–free conditions over the last two decades. The synthesis of phosphine ligands on 4,4′-bisquinolone structural framework, disubstituted phosphinic acid esters, vinyl phosphines, aryl- and vinylphosphonates, sugar and nucleoside phosphonates, aminobisphosphonates, triphenyl phosphines, water-soluble tertiary phosphine oxides and many other potentially useful organophosphorous compounds have been illustrated critically. The Hirao reaction, Michaelis-Arbuzov reaction and Sandmeyer type of reactions are generally involved in creating C-P bonds. The role of various metal catalysts, solvents, bases, additives and temperature in different literatures are carefully discussed.

scholarly journals Transition-Metal-Free, Visible-Light-Promoted C–S Cross-Coupling through Intermolecular Charge Transfer

Synlett ◽  
2018 ◽  
Vol 29 (19) ◽  
pp. 2449-2455 ◽  
Author(s):  
Garret Miyake ◽  
Bin Liu ◽  
Chern-Hooi Lim
Keyword(s):  
Transition Metal ◽  
Visible Light ◽  
Materials Science ◽  
Bond Formation ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Cross Coupling Reactions ◽  
Visible Light Driven ◽  
Metal Catalyzed ◽  
Historical Developments

C–S cross-couplings are an important class of reactions ­applied across organic synthesis, materials science, and pharma­ceuticals. Several different methodologies have been developed to achieve this significant transformation. However, currently available synthetic procedures significantly rely on transition metals. This article describes historical developments in the field of transition-metal-catalyzed C–S cross-coupling reactions, the development of a visible-light-driven and catalyst-free approach to C–S bond formation, and future outlooks.

scholarly journals Nickel-Catalyzed Ipso-Borylation of Silyloxyarenes via C–O Bond Activation

2021 ◽  
Author(s):  
Wesley Pein ◽  
Eric Wiensch ◽  
John Montgomery
Keyword(s):  
Bond Activation ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Nickel Catalysis ◽  
Silyl Ethers ◽  
Cross Coupling Reactions ◽  
Boronic Esters ◽  
Directing Group ◽  
Aromatic Systems ◽  
Oxygen Bond

A mild method to convert silyloxyarenes to pinacol boronic esters using nickel catalysis is described. In contrast to other borylation protocols of relatively inert C–O bonds, the method is competent in activating the carbon-oxygen bond of silyloxyarenes in isolated aromatic systems lacking a directing group. The catalytic functionalization of benzyl silyl ethers was also achieved under these conditions. Orthogonal reactivity of silyloxyarenes vs other electrophiles was demonstrated in the case of several cross-coupling reactions wherein the unaffected silyloxarene could be functionalized subsequently.

scholarly journals Development of Heterocycle-Substituted and Fused Azulenes in the Last Decade (2010–2020)

2020 ◽  
Vol 21 (19) ◽  
pp. 7087 ◽  
Author(s):  
Taku Shoji ◽  
Tetsuo Okujima ◽  
Shunji Ito
Keyword(s):  
Transition Metal ◽  
Physical Properties ◽  
Electrophilic Substitution ◽  
Materials Science ◽  
Cross Coupling ◽  
Synthetic Methods ◽  
Coupling Reactions ◽  
Cross Coupling Reactions ◽  
Transition Metal Catalyzed ◽  
Metal Catalyzed

Azulene derivatives with heterocyclic moieties in the molecule have been synthesized for applications in materials science by taking advantage of their unique properties. These derivatives have been prepared by various methods, involving electrophilic substitution, condensation, cyclization, and transition metal-catalyzed cross-coupling reactions. Herein, we present the development of the synthetic methods, reactivities, and physical properties for the heterocycle-substituted and heterocycle-fused azulenes reported in the last decade.

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