scholarly journals Reversible C–C Bond Formation Using Palladium Catalysis

2021 ◽  
Author(s):  
Austin Marchese ◽  
Bijan Mirabi ◽  
Colton Johnson ◽  
Mark Lautens
Keyword(s):  
Transition Metal ◽  
Palladium Catalyst ◽  
Bond Formation ◽  
Palladium Catalysis ◽  
Extensive Study ◽  
Computational Studies ◽  
Reversible Transition ◽  
New Methodologies ◽  
Catalyzed Reactions ◽  
Metal Catalyzed

Abstract A widely appreciated principle is that all reactions are fundamentally reversible. Observing reversible transition metal-catalyzed reactions, particularly those that include the cleavage of C–C bonds, are more challenging. The development of the palladium- and nickel-catalyzed carboiodination reactions afforded access to the syn- and anti-diastereomers of the iodo-dihydroisoquinolone products. Using these substrates, an extensive study investigating the catalytic reversibility of the C–C bond formation using a different palladium catalyst was undertaken. A combination of experimental and computational studies led to the discovery of a variety of new methodologies and concepts key to understanding the process of reversible C–C bond formations.

Transition-metal-catalyzed reactions of carbon-heteroatom bond formation by substitution and addition processes

2005 ◽  
Vol 77 (12) ◽  
pp. 2021-2027 ◽  
Author(s):  
Irina P. Beletskaya
Keyword(s):  
Transition Metal ◽  
Triple Bond ◽  
Bond Formation ◽  
Cross Coupling ◽  
Addition Reactions ◽  
Coupling Reactions ◽  
Cross Coupling Reactions ◽  
Transition Metal Catalyzed ◽  
Catalyzed Reactions ◽  
Metal Catalyzed

Two types of transition-metal-catalyzed cross-coupling reactions, which both lead to the formation of carbon-heteroatom bonds, are considered: RX + E-H and E-X + RM. The potential of addition reactions of E-H or E-E to double or triple bond in C-E bond formation is also demonstrated.

scholarly journals Recent advances in transition metal-catalyzed Csp2-monofluoro-, difluoro-, perfluoromethylation and trifluoromethylthiolation

2013 ◽  
Vol 9 ◽  
pp. 2476-2536 ◽  
Author(s):  
Grégory Landelle ◽  
Armen Panossian ◽  
Sergiy Pazenok ◽  
Jean-Pierre Vors ◽  
Frédéric R Leroux
Keyword(s):  
Transition Metal ◽  
Life Science ◽  
Bond Formation ◽  
Research Field ◽  
Successful Execution ◽  
The Subject ◽  
Transition Metal Catalyzed ◽  
Catalyzed Reactions ◽  
Metal Catalyzed ◽  
Oriented Research

In the last few years, transition metal-mediated reactions have joined the toolbox of chemists working in the field of fluorination for Life-Science oriented research. The successful execution of transition metal-catalyzed carbon–fluorine bond formation has become a landmark achievement in fluorine chemistry. This rapidly growing research field has been the subject of some excellent reviews. Our approach focuses exclusively on transition metal-catalyzed reactions that allow the introduction of –CFH2, –CF2H, –C n F2 n +1 and –SCF3 groups onto sp² carbon atoms. Transformations are discussed according to the reaction-type and the metal employed. The review will not extend to conventional non-transition metal methods to these fluorinated groups.

Carbon-carbon bond-forming reactions using alkyl fluorides

2008 ◽  
Vol 80 (5) ◽  
pp. 941-951 ◽  
Author(s):  
Jun Terao ◽  
Hirohisa Todo ◽  
Hiroyasu Watabe ◽  
Aki Ikumi ◽  
Yoshiaki Shinohara ◽  
...  
Keyword(s):  
Transition Metal ◽  
Bond Formation ◽  
Transition Metal Catalysts ◽  
Grignard Reagents ◽  
Bond Forming ◽  
Carbon Carbon Bond ◽  
Catalyzed Reactions ◽  
Metal Catalyzed ◽  
Alkyl Fluorides ◽  
Bond Formation Reactions

This account reviews C-C bond formation reactions using alkyl fluorides mostly focusing on the transition-metal-catalyzed reactions. These reactions proceed efficiently under mild conditions by the combined use of Grignard reagents and transition-metal catalysts, such as Ni, Cu, and Zr. It is proposed that ate complex intermediates formed by the reaction of these transition metals with Grignard reagents play important roles as the active catalytic species. Organoaluminun reagents react directly with alkyl fluorides in nonpolar solvents at room temperature to form C-C bonds. These studies demonstrate the practical usefulness of alkyl fluorides in C-C bond formation reactions and provide a promising method for the construction of carbon frameworks employing alkyl fluorides. The scope and limitations, as well as reaction pathways, are discussed.

scholarly journals Recent Advances in Transition-Metal-Catalyzed, Directed Aryl C–H/N–H Cross-Coupling Reactions

Synthesis ◽  
2017 ◽  
Vol 49 (20) ◽  
pp. 4586-4598 ◽  
Author(s):  
Martyn Henry ◽  
Mohamed Mostafa ◽  
Andrew Sutherland
Keyword(s):  
Transition Metal ◽  
Bond Formation ◽  
Coupling Reaction ◽  
Cross Coupling ◽  
Short Review ◽  
Coupling Reactions ◽  
Dehydrogenative Coupling ◽  
Transition Metal Catalyzed ◽  
Catalyzed Reactions ◽  
Metal Catalyzed

Amination and amidation of aryl compounds using a transition-metal-catalyzed cross-coupling reaction typically involves prefunctionalization or preoxidation of either partner. In recent years, a new class of transition-metal-catalyzed cross-dehydrogenative coupling reaction has been developed for the direct formation of aryl C–N bonds. This short review highlights the substantial progress made for ortho-C–N bond formation via transition-metal-catalyzed chelation-directed aryl C–H activation and gives an overview of the challenges that remain for directed meta- and para-selective reactions.1 Introduction2 Intramolecular C–N Cross-Dehydrogenative Coupling2.1 Nitrogen Functionality as Both Coupling Partner and Directing Group2.2 Chelating-Group-Directed Intramolecular C–N Bond Formation3 Intermolecular C–N Cross-Dehydrogenative Coupling3.1 ortho-C–N Bond Formation3.1.1 Copper-Catalyzed Reactions3.1.2 Other Transition-Metal-Catalyzed Reactions3.2 meta- and para-C–N Bond Formation4 C–N Cross-Dehydrogenative Coupling of Acidic C–H Bonds5 Conclusions

Carbon Dioxide-Mediated C(sp2)–H Arylation of Primary and Secondary Benzylamines

2018 ◽  
Author(s):  
Mohit Kapoor ◽  
Pratibha Chand-Thakuri ◽  
Michael Young
Keyword(s):  
Carbon Dioxide ◽  
Transition Metal ◽  
Bond Activation ◽  
Bond Formation ◽  
Carbon Bond ◽  
Chelate Effect ◽  
Free Amine ◽  
Carbon Carbon Bond ◽  
New Strategy ◽  
Metal Catalyzed

Carbon-carbon bond formation by transition metal-catalyzed C–H activation has become an important strategy to fabricate new bonds in a rapid fashion. Despite the pharmacological importance of <i>ortho</i>-arylbenzylamines, however, effective <i>ortho</i>-C–C bond formation from C–H bond activation of free primary and secondary benzylamines using Pd<sup>II</sup> remains an outstanding challenge. Presented herein is a new strategy for constructing <i>ortho</i>-arylated primary and secondary benzylamines mediated by carbon dioxide (CO<sub>2</sub>). The use of CO<sub>2</sub> is critical to allowing this transformation to proceed under milder conditions than previously reported, and that are necessary to furnish free amine products that can be directly used or elaborated without the need for deprotection. In cases where diarylation is possible, a chelate effect is demonstrated to facilitate selective monoarylation.

Monodentate Trialkylphosphines: Privileged Ligands in Metal-catalyzed Crosscoupling Reactions

2020 ◽  
Vol 24 (3) ◽  
pp. 231-264 ◽  
Author(s):  
Kevin H. Shaughnessy
Keyword(s):  
Transition Metal ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Cross Coupling Reactions ◽  
Aryl Bromides ◽  
Wide Range ◽  
Sterically Demanding ◽  
Transition Metal Catalyzed ◽  
Catalyzed Reactions ◽  
Metal Catalyzed

Phosphines are widely used ligands in transition metal-catalyzed reactions. Arylphosphines, such as triphenylphosphine, were among the first phosphines to show broad utility in catalysis. Beginning in the late 1990s, sterically demanding and electronrich trialkylphosphines began to receive attention as supporting ligands. These ligands were found to be particularly effective at promoting oxidative addition in cross-coupling of aryl halides. With electron-rich, sterically demanding ligands, such as tri-tertbutylphosphine, coupling of aryl bromides could be achieved at room temperature. More importantly, the less reactive, but more broadly available, aryl chlorides became accessible substrates. Tri-tert-butylphosphine has become a privileged ligand that has found application in a wide range of late transition-metal catalyzed coupling reactions. This success has led to the use of numerous monodentate trialkylphosphines in cross-coupling reactions. This review will discuss the general properties and features of monodentate trialkylphosphines and their application in cross-coupling reactions of C–X and C–H bonds.

Chemistry of Unsymmetrical C1-Substituted Oxabenzonorbornadienes

2021 ◽  
Vol 17 ◽  
Author(s):  
Austin Pounder ◽  
Angel Ho ◽  
Matthew Macleod ◽  
William Tam
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Substituent Effects ◽  
Face Selectivity ◽  
Transition Metal Catalyzed ◽  
Catalyzed Reactions ◽  
Metal Catalyzed ◽  
Synthetic Intermediate

: Oxabenzonorbornadiene (OBD) is a useful synthetic intermediate which can be readily activated by transition metal complexes with great face selectivity due to its dual-faced nature and intrinsic angle strain on the alkene. To date, the understanding of transition-metal catalyzed reactions of OBD itself has burgeoned; however, this has not been the case for unsymmetrical OBDs. Throughout the development of these reactions, the nature of C1-substituent has proven to have a profound effect on both the reactivity and selectivity of the outcome of the reaction. Upon substitution, different modes of reactivity arise, contributing to the possibility of multiple stereo-, regio-, and in extreme cases, constitutional isomers which can provide unique means of constructing a variety of synthetically useful cyclic frameworks. To maximize selectivity, an understanding of bridgehead substituent effects is crucial. To that end, this review outlines hitherto reported examples of bridgehead substituent effects on the chemistry of unsymmetrical C1-substituted OBDs.

Recent advance in NHC-palladium catalysis for alkynes chemistry: versatile synthesis and applications

2021 ◽  
Author(s):  
Jianxiao Li ◽  
Dan He ◽  
Zidong Lin ◽  
Wanqing Wu ◽  
Huanfeng Jiang
Keyword(s):  
Transition Metal ◽  
Palladium Catalysis ◽  
Metal Catalysts ◽  
Chemical Transformations ◽  
The Past ◽  
Transition Metal Catalyzed ◽  
Metal Catalyzed

During the past decades, alkynes chemistry has attracted considerable attention owing to their unique and idiographic nucleophilic and electrophilic properties in transition-metal-catalyzed chemical transformations. Among the various metal catalysts, palladium...

scholarly journals Transition metal-catalyzed reactions of N-sulfinyl imines

2021 ◽  
pp. 153104
Author(s):  
Francisco Foubelo ◽  
Carmen Nájera ◽  
José M. Sansano ◽  
Miguel Yus
Keyword(s):  
Transition Metal ◽  
Transition Metal Catalyzed ◽  
Catalyzed Reactions ◽  
Metal Catalyzed
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