Journal ArticleDOI
Copper-Catalyzed Aerobic Oxidative C ? H Functionalizations: Trends and Mechanistic Insights
TLDR
This work has reported several recently reported Cu-catalyzed C-H oxidation reactions that feature substrates that are electron-deficient or appear unlikely to undergo single-electron transfer to copper(II), and evidence has been obtained for the involvement of organocopper(III) intermediates in the reaction mechanism.Abstract:
The selective oxidation of C-H bonds and the use of O(2) as a stoichiometric oxidant represent two prominent challenges in organic chemistry. Copper(II) is a versatile oxidant, capable of promoting a wide range of oxidative coupling reactions initiated by single-electron transfer (SET) from electron-rich organic molecules. Many of these reactions can be rendered catalytic in Cu by employing molecular oxygen as a stoichiometric oxidant to regenerate the active copper(II) catalyst. Meanwhile, numerous other recently reported Cu-catalyzed C-H oxidation reactions feature substrates that are electron-deficient or appear unlikely to undergo single-electron transfer to copper(II). In some of these cases, evidence has been obtained for the involvement of organocopper(III) intermediates in the reaction mechanism. Organometallic C-H oxidation reactions of this type represent important new opportunities for the field of Cu-catalyzed aerobic oxidations.read more
Citations
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Journal ArticleDOI
Controlling the Catalytic Aerobic Oxidation of Phenols
TL;DR: Conditions for the ortho-oxygenation or oxidative coupling of phenols under copper (Cu)-catalyzed aerobic conditions that give rise to Ortho-quinones, biphenols or benzoxepines are described and each product class can be accessed selectively by the appropriate choice of Cu(I) salt, amine ligand, desiccant and reaction temperature.
Journal ArticleDOI
Tandem isomerization and C-H activation: regioselective hydroheteroarylation of allylarenes.
TL;DR: The first Ni-promoted prototype reaction based on the tandem C-H activation of heteroarenes with alkene isomerization is demonstrated, leading to the branched hydroheteroarylation products.
Journal ArticleDOI
Factors That Control C-C Cleavage versus C-H Bond Hydroxylation in Copper-Catalyzed Oxidations of Ketones with O2.
TL;DR: The role of hppH is uncovered to act not only as a base in the transformation but also as a reductant of the peroxide to the corresponding α-hydroxy ketone, allowing the tuning of reduction efficiency toward higher driving forces, if required.
Journal ArticleDOI
Amine-accelerated manganese-catalyzed aromatic C–H conjugate addition to α,β-unsaturated carbonyls
TL;DR: Experimental and computational studies substantiated the validity of the proposed catalytic cycle and described the first manganese-catalyzed one-step direct aromatic C-H conjugate addition to α,β-unsaturated carbonyls.
Journal ArticleDOI
Enantioselective Oxidative Cross-Dehydrogenative Coupling of Tertiary Amines to Aldehydes**
TL;DR: An enantioselective oxidative coupling reaction of aldehydes and tertiary amines under cooperative amine and metal catalysis is reported, which indicates that DMF is a good solvent and CuBr2 is an effective metal catalyst.
References
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Journal ArticleDOI
Palladium-Catalyzed Ligand-Directed C−H Functionalization Reactions
TL;DR: This is the first comprehensive review encompassing the large body of work in this field over the past 5 years, and will focus specifically on ligand-directed C–H functionalization reactions catalyzed by palladium.
Journal ArticleDOI
Palladium(II)-catalyzed C-H activation/C-C cross-coupling reactions: versatility and practicality.
TL;DR: A review of palladium-catalyzed coupling of CH bonds with organometallic reagents through a PdII/Pd0 catalytic cycle can be found in this paper.
Journal ArticleDOI
Catalytic dehydrogenative cross-coupling: forming carbon-carbon bonds by oxidizing two carbon-hydrogen bonds
Charles S. Yeung,Vy M. Dong +1 more
Journal ArticleDOI
Multicopper Oxidases and Oxygenases
TL;DR: Copper sites have historically been divided into three classes based on their spectroscopic features, which reflect the geometric and electronic structure of the active site: type 1 or blue copper, type 2 (T2) or normal copper, and type 3 (T3) or coupled binuclear copper centers.
Journal ArticleDOI
Rhodium-Catalyzed C-C Bond Formation via Heteroatom-Directed C-H Bond Activation
TL;DR: This review focuses on Rh-catalyzed methods for C-H bond functionalization, which have seen widespread success over the course of the last decade and are discussed in detail in the accompanying articles in this special issue of Chemical Reviews.
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