Chromium-Catalyzed Cross-Coupling Reactions by Selective Activation of Chemically Inert Aromatic C−O, C−N and C−H Bonds

Earth Abundant ◽

Transition-metal-catalyzed cross-coupling has appeared as one of powerful and useful tools in the formation of C–C and C–heteroatom bonds. Given that the resource of precious metals on earth is shortage, the use of earth-abundant metals as catalysts in developing cost-effective strategies of cross-coupling is one of trends to synthetic chemistry. Compared with the achievements using first-row metal catalysis of nickel, iron, cobalt, and even manganese, the group 6 metal chromium has rarely been used in promoting cross-coupling. This perspective will cover recent advances in Cr-catalyzed cross-coupling reactions by the transformations of chemically inert C(aryl)–O, C(aryl)–N and C(aryl)–H bonds, offering selective strategies for molecule construction. The ability of low-valent Cr with a high-spin state involving in the process of two-electron oxidative addition will be highlighted, which is different with the mechanism by single-electron-transfer that is traditionally proposed in chromium-mediated transformations. 1 Introduction 2 Cr-Catalyzed Kumada Coupling of Unactivated C(aryl)−O and C(aryl)−N Bonds 3 Cr-Catalyzed Reductive Cross-Coupling between Two Unactivated C(aryl)–Heteroatom Bonds 4 Cr-Catalyzed Functionalization of Unactivated C(aryl)–H Bonds 5 Conclusion and Outlook

Monodentate Trialkylphosphines: Privileged Ligands in Metal-catalyzed Crosscoupling Reactions

Current Organic Chemistry ◽

10.2174/1385272824666200211114540 ◽

2020 ◽

Vol 24 (3) ◽

pp. 231-264 ◽

Cited By ~ 3

Author(s):

Kevin H. Shaughnessy

Keyword(s):

Transition Metal ◽

Cross Coupling ◽

Coupling Reactions ◽

Aryl Bromides ◽

Wide Range ◽

Sterically Demanding ◽

Transition Metal Catalyzed ◽

Catalyzed Reactions ◽

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.

Synthesis of Marine Polyacetylenes Callyberynes A−C by Transition-Metal-Catalyzed Cross-Coupling Reactions to sp Centers

The Journal of Organic Chemistry ◽

10.1021/jo052609u ◽

2006 ◽

Vol 71 (7) ◽

pp. 2802-2810 ◽

Cited By ~ 32

Author(s):

Susana López ◽

Francisco Fernández-Trillo ◽

Pilar Midón ◽

Luis Castedo ◽

Carlos Saá

Keyword(s):

Transition Metal ◽

Cross Coupling ◽

Coupling Reactions ◽

Transition Metal Catalyzed ◽

Metal-Catalyzed Cross-Coupling Reactions and More. 3 Volume Set. Edited by Armin de Meijere, Stefan Bräse and Martin Oestreich.

Angewandte Chemie International Edition ◽

10.1002/anie.201408267 ◽

2014 ◽

Vol 53 (48) ◽

pp. 13001-13002 ◽

Cited By ~ 2

Author(s):

Ian J. S. Fairlamb

Keyword(s):

Cross Coupling ◽

Coupling Reactions ◽

Protecting group-free, selective cross-coupling of alkyltrifluoroborates with borylated aryl bromides via photoredox/nickel dual catalysis

Proceedings of the National Academy of Sciences ◽

10.1073/pnas.1509715112 ◽

2015 ◽

Vol 112 (39) ◽

pp. 12026-12029 ◽

Cited By ~ 66

Author(s):

Yohei Yamashita ◽

John C. Tellis ◽

Gary A. Molander

Keyword(s):

Small Molecules ◽

Functional Group ◽

Cross Coupling ◽

Differential Protection ◽

Coupling Reactions ◽

Protecting Group ◽

Aryl Bromides ◽

Rapid Construction ◽

Orthogonal reactivity modes offer substantial opportunities for rapid construction of complex small molecules. However, most strategies for imparting orthogonality to cross-coupling reactions rely on differential protection of reactive sites, greatly reducing both atom and step economies. Reported here is a strategy for orthogonal cross-coupling wherein a mechanistically distinct activation mode for transmetalation of sp3-hybridized organoboron reagents enables C-C bond formation in the presence of various protected and unprotected sp2-hybridized organoborons. This manifold has the potential for broad application, because orthogonality is inherent to the activation mode itself. The diversification potential of this platform is shown in the rapid elaboration of a trifunctional lynchpin through various transition metal-catalyzed processes without nonproductive deprotection or functional group manipulation steps.

Stereochemistry of transition-metal-catalyzed cross-coupling reactions

The Journal of Organic Chemistry ◽

10.1021/jo00338a004 ◽

1981 ◽

Vol 46 (25) ◽

pp. 5074-5077 ◽

Cited By ~ 21

Author(s):

H. M. Walborsky ◽

R. Bruce Banks

Keyword(s):

Transition Metal ◽

Cross Coupling ◽

Coupling Reactions ◽

Transition Metal Catalyzed ◽

Nach Überarbeitung empfehlenswert: Metal-catalyzed Cross-coupling Reactions. Hrsg. von F. Diederich, P. J. Stang. Wiley-VCH, Weinheim, 1998. 518 S., geb., 248,- DM. ISBN 3-527-29421-X

Nachrichten aus Chemie Technik und Laboratorium ◽

10.1002/nadc.19990470525 ◽

1999 ◽

Vol 47 (5) ◽

pp. 573-573

Author(s):

Juan Almena

Keyword(s):

Cross Coupling ◽

Coupling Reactions ◽

Copper’s rapid ascent in visible-light photoredox catalysis

Science ◽

10.1126/science.aav9713 ◽

2019 ◽

Vol 364 (6439) ◽

pp. eaav9713 ◽

Cited By ~ 107

Author(s):

Asik Hossain ◽

Aditya Bhattacharyya ◽

Oliver Reiser

Keyword(s):

Visible Light ◽

Organic Dyes ◽

Low Cost ◽

Cross Coupling ◽

Coupling Reactions ◽

Photoredox Catalysis ◽

Rapid Ascent ◽

Catalyzed Reactions ◽

Visible-light photoredox catalysis offers a distinct activation mode complementary to thermal transition metal catalyzed reactions. The vast majority of photoredox processes capitalizes on precious metal ruthenium(II) or iridium(III) complexes that serve as single-electron reductants or oxidants in their photoexcited states. As a low-cost alternative, organic dyes are also frequently used but in general suffer from lower photostability. Copper-based photocatalysts are rapidly emerging, offering not only economic and ecological advantages but also otherwise inaccessible inner-sphere mechanisms, which have been successfully applied to challenging transformations. Moreover, the combination of conventional photocatalysts with copper(I) or copper(II) salts has emerged as an efficient dual catalytic system for cross-coupling reactions.