Recent Progress in Nickel-Catalyzed Biaryl Coupling
01 Jan 2013-European Journal of Organic Chemistry (John Wiley & Sons, Ltd)-Vol. 2013, Iss: 1, pp 19-30
TL;DR: This work describes recent developments in nickel-catalyzed biaryl coupling methodology, along with mechanistic studies and applications that focus on nickel-Catalyzed coupling reactions in which “unreactive” bonds are converted into biaryl moieties.
About: This article is published in European Journal of Organic Chemistry.The article was published on 2013-01-01. It has received 436 citations till now. The article focuses on the topics: Homogeneous catalysis.
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TL;DR: It would, therefore, appear that direct functionalization of substrates by activation of C-H bonds would eliminate the multiple steps and limitations associated with the preparation of functionalized starting materials.
Abstract: C-H bonds are ubiquitous in organic compounds. It would, therefore, appear that direct functionalization of substrates by activation of C-H bonds would eliminate the multiple steps and limitations associated with the preparation of functionalized starting materials. Regioselectivity is an important issue because organic molecules can contain a wide variety of C-H bonds. The use of a directing group can largely overcome the issue of regiocontrol by allowing the catalyst to come into proximity with the targeted C-H bonds. A wide variety of functional groups have been evaluated for use as directing groups in the transformation of C-H bonds. In 2005, Daugulis reported the arylation of unactivated C(sp(3))-H bonds by using 8-aminoquinoline and picolinamide as bidentate directing groups, with Pd(OAc)2 as the catalyst. Encouraged by these promising results, a number of transformations of C-H bonds have since been developed by using systems based on bidentate directing groups. In this Review, recent advances in this area are discussed.
1,719 citations
TL;DR: Some of the most recent and significant developments in homogeneous nickel catalysis are discussed, with an emphasis on both synthetic outcome and mechanism.
Abstract: Tremendous advances have been made in nickel catalysis over the past decade Several key properties of nickel, such as facile oxidative addition and ready access to multiple oxidation states, have allowed the development of a broad range of innovative reactions In recent years, these properties have been increasingly understood and used to perform transformations long considered exceptionally challenging Here we discuss some of the most recent and significant developments in homogeneous nickel catalysis, with an emphasis on both synthetic outcome and mechanism
1,487 citations
Cites background from "Recent Progress in Nickel-Catalyzed..."
...The synthesis of triarylmethanes (17) can be achieved by catalytic Ni(cod)2 and PCy3 or SIMes—the stereoselectivity (retention or inversion, respectively 17a or 17b) is determined by the identity of the ligand....
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TL;DR: Recent progress in the field of organometallic cobalt-catalyzed C–H activation is reviewed until November 2015.
Abstract: Catalytic C–H activation has emerged as a powerful tool for sustainable syntheses. In the recent years, notable success was achieved with the development of cobalt-catalyzed C–H functionalizations with either in situ generated or single-component cobalt-complexes under mild reaction conditions. Herein, recent progress in the field of organometallic cobalt-catalyzed C–H activation is reviewed until November 2015.
953 citations
TL;DR: This review provides a comprehensive overview of the fundamentals and applications of transition metal-mediated/catalyzed oxidative C-H/C-H coupling reactions between two (hetero)arenes.
Abstract: Transition metal-mediated C–H bond activation and functionalization represent one of the most straightforward and powerful tools in modern organic synthetic chemistry. Bi(hetero)aryls are privileged π-conjugated structural cores in biologically active molecules, organic functional materials, ligands, and organic synthetic intermediates. The oxidative C–H/C–H coupling reactions between two (hetero)arenes through 2-fold C–H activation offer a valuable opportunity for rapid assembly of diverse bi(hetero)aryls and further exploitation of their applications in pharmaceutical and material sciences. This review provides a comprehensive overview of the fundamentals and applications of transition metal-mediated/catalyzed oxidative C–H/C–H coupling reactions between two (hetero)arenes. The substrate scope, limitation, reaction mechanism, regioselectivity, and chemoselectivity, as well as related control strategies of these reactions are discussed. Additionally, the applications of these established methods in the s...
822 citations
TL;DR: This review broadly discusses various C-H bond functionalization reactions for the formation of C-C bonds with the aid of bidentate directing groups.
Abstract: During the past decades, synthetic organic chemistry discovered that directing group assisted C–H activation is a key tool for the expedient and siteselective construction of C–C bonds. Among the v...
573 citations
References
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3,281 citations
TL;DR: A number of improvements have developed the former process into an industrially very useful and attractive method for the construction of aryl -aryl bonds, but the need still exists for more efficient routes whereby the same outcome is accomplished, but with reduced waste and in fewer steps.
Abstract: The biaryl structural motif is a predominant feature in many pharmaceutically relevant and biologically active compounds. As a result, for over a century 1 organic chemists have sought to develop new and more efficient aryl -aryl bond-forming methods. Although there exist a variety of routes for the construction of aryl -aryl bonds, arguably the most common method is through the use of transition-metalmediated reactions. 2-4 While earlier reports focused on the use of stoichiometric quantities of a transition metal to carry out the desired transformation, modern methods of transitionmetal-catalyzed aryl -aryl coupling have focused on the development of high-yielding reactions achieved with excellent selectivity and high functional group tolerance under mild reaction conditions. Typically, these reactions involve either the coupling of an aryl halide or pseudohalide with an organometallic reagent (Scheme 1), or the homocoupling of two aryl halides or two organometallic reagents. Although a number of improvements have developed the former process into an industrially very useful and attractive method for the construction of aryl -aryl bonds, the need still exists for more efficient routes whereby the same outcome is accomplished, but with reduced waste and in fewer steps. In particular, the obligation to use coupling partners that are both activated is wasteful since it necessitates the installation and then subsequent disposal of stoichiometric activating agents. Furthermore, preparation of preactivated aryl substrates often requires several steps, which in itself can be a time-consuming and economically inefficient process.
3,204 citations
TL;DR: Investigations revealed that the conversion of C-H bonds to C-B bonds was both thermodynamically and kinetically favorable and highlighted the accessible barriers for C- H bond cleavage and B-C bond formation during the borylation of alkanes and arenes.
Abstract: A number of studies were conducted to demonstrate C-H activation for the construction of C-B bonds. Investigations revealed that the conversion of C-H bonds to C-B bonds was both thermodynamically and kinetically favorable. The reaction at a primary C-H bond of methane or a higher alkene B 2(OR)4 formed an alkylboronate ester R' -B(OR)2 and the accompanying borane H-B(OR2. The ester and the borane were formed on the basis of calculated bond energies for methylboronates and dioaborolanes. The rates of key steps along the reaction pathway for the conversion of a C-H bond in an alkane or arene to the C-B bond in an alkyl or arylboronate ester were favorable. These studies also highlighted the accessible barriers for C-H bond cleavage and B-C bond formation during the borylation of alkanes and arenes.
2,108 citations
TL;DR: In this paper, the authors used Pd2(dba)3/P(t-Bu)3 as a catalyst for Suzuki cross-coupling of aryl and vinyl triflates.
Abstract: Through the use of Pd2(dba)3/P(t-Bu)3 as a catalyst, a wide range of aryl and vinyl halides, including chlorides, undergo Suzuki cross-coupling with arylboronic acids in very good yield, typically at room temperature; through use of Pd(OAc)2/PCy3, a diverse array of aryl and vinyl triflates react cleanly at room temperature. Together, these two catalyst systems cover a broad spectrum of commonly encountered substrates for Suzuki couplings. Furthermore, they display novel reactivity patterns, such as the selective cross-coupling by Pd2(dba)3/P(t-Bu)3 of an aryl chloride in preference to an aryl triflate, and they can be used at low loading, even for reactions of aryl chlorides. Preliminary mechanistic work indicates that a palladium monophosphine complex is the active catalyst in the cross-coupling of aryl halides.
1,413 citations
TL;DR: Nickel-Catalyzed Cross-Couplings Involving Carbon-Oxygen Bonds Brad M. Rosen, Kyle W. Quasdorf, Daniella A. Wilson, Na Zhang, Ana-Maria Resmerita, Neil K. Garg, and Virgil Percec report on cross-coupling strategies for high-performance liquid chromatography of carbon dioxide and nitrogen.
Abstract: Nickel-Catalyzed Cross-Couplings Involving Carbon-Oxygen Bonds Brad M. Rosen, Kyle W. Quasdorf, Daniella A. Wilson, Na Zhang, Ana-Maria Resmerita, Neil K. Garg,* and Virgil Percec* Roy & Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, United States Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, United States
1,100 citations