A fundamental aim in the field of catalysis is the development of new modes of small molecule activation. One approach toward the catalytic activation of organic molecules that has received much attention recently is visible light photoredox catalysis. In a general sense, this approach relies on the ability of metal complexes and organic dyes to engage in single-electron-transfer (SET) processes with organic substrates upon photoexcitation with visible light.

Many of the most commonly employed visible light photocatalysts are polypyridyl complexes of ruthenium and iridium, and are typified by the complex tris(2,2′-bipyridine) ruthenium(II), or Ru(bpy)32+ (Figure 1). These complexes absorb light in the visible region of the electromagnetic spectrum to give stable, long-lived photoexcited states.1,2 The lifetime of the excited species is sufficiently long (1100 ns for Ru(bpy)32+) that it may engage in bimolecular electron-transfer reactions in competition with deactivation pathways.3 Although these species are poor single-electron oxidants and reductants in the ground state, excitation of an electron affords excited states that are very potent single-electron-transfer reagents. Importantly, the conversion of these bench stable, benign catalysts to redox-active species upon irradiation with simple household lightbulbs represents a remarkably chemoselective trigger to induce unique and valuable catalytic processes.






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Figure 1


Ruthenium polypyridyl complexes: versatile visible light photocatalysts.

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Visible Light Photoredox Catalysis with Transition Metal Complexes: Applications in Organic Synthesis

Catalytic dehydrogenative cross-coupling: forming carbon-carbon bonds by oxidizing two carbon-hydrogen bonds

The study of biomolecules in their native environments is a challenging task because of the vast complexity of cellular systems. Technologies developed in the last few years for the selective modification of biological species in living systems have yielded new insights into cellular processes. Key to these new techniques are bioorthogonal chemical reactions, whose components must react rapidly and selectively with each other under physiological conditions in the presence of the plethora of functionality necessary to sustain life. Herein we describe the bioorthogonal chemical reactions developed to date and how they can be used to study biomolecules.

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Bioorthogonal Chemistry: Fishing for Selectivity in a Sea of Functionality

The chemistry of heterocyclic carbenes has experienced a rapid development over the last years. In addition to the imidazolin-2-ylidenes, a large number of cyclic diaminocarbenes with different ring sizes have been described. Aside from diaminocarbenes, P-heterocyclic carbenes, and derivatives with only one, or even no heteroatom within the carbene ring are known. New methods for the synthesis of complexes with N-heterocyclic carbene ligands such as the oxidative addition or the metal atom template controlled cyclization of β-functionalized isocyanides have been developed recently. This review summarizes the new developments regarding the synthesis of N-heterocyclic carbenes and their metal complexes.

Heterocyclic Carbenes: Synthesis and Coordination Chemistry

In 2010, Richard Heck, Ei-ichi Negishi, and Akira Suzuki joined the prestigious circle of Nobel Laureate chemists for their roles in discovering and developing highly practical methodologies for C-C bond construction. From their original contributions in the early 1970s the landscape of the strategies and methods of organic synthesis irreversibly changed for the modern chemist, both in academia and in industry. In this Review, we attempt to trace the historical origin of these powerful reactions, and outline the developments from the seminal discoveries leading to their eminent position as appreciated and applied today.

Palladium-Catalyzed Cross-Coupling: A Historical Contextual Perspective to the 2010 Nobel Prize

Computational Studies of Synthetically Relevant Homogeneous Organometallic Catalysis Involving Ni, Pd, Ir, and Rh: An Overview of Commonly Employed DFT Methods and Mechanistic Insights

The reversal of regioselectivity in a Pd-catalyzed cross-coupling reaction of an aryl chloro triflate with different ligands, established by Fu and co-workers, has been studied computationally. C-O insertion was found to be controlled by Pd-HOMO ArO-LUMO interaction, where C-Cl insertion is facilitated by the lower C-Cl TS distortion energy. The greater reactivities of monoligated Pd species are due primarily to the lack of distortion of the Pd species.

Ligand-Controlled Regioselectivity in Palladium-Catalyzed Cross Coupling Reactions

A catalytic protocol to convert aryl and heteroaryl chlorides to the corresponding trifluoromethyl sulfides is reported herein. It relies on a relatively inexpensive Ni(cod)2/dppf (cod = 1,5-cyclooctadiene; dppf = 1,1′-bis(diphenylphosphino)ferrocene) catalyst system and the readily accessible coupling reagent (Me4N)SCF3. Our computational and experimental mechanistic data are consistent with a Ni(0)/Ni(II) cycle and inconsistent with Ni(I) as the reactive species. The relevant intermediates were prepared, characterized by X-ray crystallography, and tested for their catalytic competence. This revealed that a monomeric tricoordinate Ni(I) complex is favored for dppf and Cl whose role was unambiguously assigned as being an off-cycle catalyst deactivation product. Only bidentate ligands with wide bite angles (e.g., dppf) are effective. These bulky ligands render the catalyst resting state as [(P–P)Ni(cod)]. The latter is more reactive than Ni(P–P)2, which was found to be the resting state for ligands with sm...

Fundamental Studies and Development of Nickel-Catalyzed Trifluoromethylthiolation of Aryl Chlorides: Active Catalytic Species and Key Roles of Ligand and Traceless MeCN Additive Revealed

The transition states and activation barriers of the 1,3-dipolar cycloadditions of azides with cycloalkynes and cycloalkenes were explored using B3LYP density functional theory (DFT) and spin component scaled SCS-MP2 methods. A survey of benzyl azide cycloadditions to substituted cyclooctynes (OMe, Cl, F, CN) showed that fluorine substitution has the most dramatic effect on reactivity. Azide cycloadditions to 3-substituted cyclooctynes prefer 1,5-addition regiochemistry in the gas phase, but CPCM solvation abolishes the regioselectivity preference, in accord with experiments in solution. The activation energies for phenyl azide addition to cycloalkynes decrease considerably as the ring size is decreased (cyclononyne ΔG⧧ = 29.2 kcal/mol, cyclohexyne ΔG⧧ = 14.1 kcal/mol). The origin of this trend is explained by the distortion/interaction model. Cycloalkynes are predicted to be significantly more reactive dipolarophiles than cycloalkenes. The activation barriers for the cycloadditions of phenyl azide and pi...

Reactivity and regioselectivity in 1,3-dipolar cycloadditions of azides to strained alkynes and alkenes: a computational study.

Suzuki coupling of the bifunctional substrate 1 using [Pd(2)(dba)(3)]/PtBu(3) gives selectivity for C-Cl in nonpolar solvents but for C-OTf in polar solvents. The results of computational and experimental studies suggest that the catalytically active species in polar solvents under conditions employing coordinating additives is inconsistent with monoligated [Pd(PtBu(3))]. Instead, the data are consistent with an anionic palladium complex as the active species.

Franziska Schoenebeck

Papers

Computational Studies of Synthetically Relevant Homogeneous Organometallic Catalysis Involving Ni, Pd, Ir, and Rh: An Overview of Commonly Employed DFT Methods and Mechanistic Insights

Ligand-Controlled Regioselectivity in Palladium-Catalyzed Cross Coupling Reactions

Fundamental Studies and Development of Nickel-Catalyzed Trifluoromethylthiolation of Aryl Chlorides: Active Catalytic Species and Key Roles of Ligand and Traceless MeCN Additive Revealed

Reactivity and regioselectivity in 1,3-dipolar cycloadditions of azides to strained alkynes and alkenes: a computational study.

Solvent Effect on Palladium‐Catalyzed Cross‐Coupling Reactions and Implications on the Active Catalytic Species