Schiff base ligands are considered “privileged ligands” because they are easily prepared by the condensation between aldehydes and imines. Stereogenic centres or other elements of chirality (planes, axes) can be introduced in the synthetic design. Schiff base ligands are able to coordinate many different metals, and to stabilize them in various oxidation states, enabling the use of Schiff base metal complexes for a large variety of useful catalytic transformations. Practical guidelines for the preparation and use of different Schiff base metal complexes in the field of catalytic transformations are discussed in this tutorial review.

Metal–Salen Schiff base complexes in catalysis: practical aspects

The area of catalysis of radical reactions has recently flourished. Various reaction conditions have been discovered and explained in terms of catalytic cycles. These cycles rarely stand alone as unique paths from substrates to products. Instead, most radical reactions have innate chains which form products without any catalyst. How do we know if a species added in "catalytic amounts" is a catalyst, an initiator, or something else? Herein we critically address both catalyst-free and catalytic radical reactions through the lens of radical chemistry. Basic principles of kinetics and thermodynamics are used to address problems of initiation, propagation, and inhibition of radical chains. The catalysis of radical reactions differs from other areas of catalysis. Whereas efficient innate chain reactions are difficult to catalyze because individual steps are fast, both inefficient chain processes and non-chain processes afford diverse opportunities for catalysis, as illustrated with selected examples.

Catalysis of Radical Reactions: A Radical Chemistry Perspective.

Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry and Green Chemistry Center, Peking University, 202 Chengfu Road, 098#, Beijing 100871, China State Key Laboratory of Organometallic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 200060, China

Transition-Metal-Free Coupling Reactions

Odd-electron, redox-active ligands are discussed in the context of catalysis. We focus on ligand-based, non-singlet state intermediates and their participation in catalytic processes and related stoichiometric transformations.

Redox-active ligands in catalysis

This Perspective illustrates the defining characteristics of free radical chemistry, beginning with its rich and storied history. Studies from our laboratory are discussed along with recent developments emanating from others in this burgeoning area. The practicality and chemoselectivity of radical reactions enable rapid access to molecules of relevance to drug discovery, agrochemistry, material science, and other disciplines. Thus, these reactive intermediates possess inherent translational potential, as they can be widely used to expedite scientific endeavors for the betterment of humankind.

Radicals: Reactive Intermediates with Translational Potential

reactions constituted an important breakthrough in the application of radical chemistry in organic synthesis.2 An important and very attractive feature of these reactions is their high degree of functional group tolerance. Since radicals are usually stable under protic conditions, alcohols or even water can, in principle, be used as solvents in radical chemistry. Consequently, protic functional groups do not need protection. As soon as the underlying principles of the kinetic and thermodynamic behavior of free radicals were firmly established, efficient synthetic applications became feasible.3 The use of chain reactions has resulted in a number of very impressive total syntheses of natural products. An example is shown in eq 1.4 The characteristic features of free radicals can by now be deduced from ESR data.5 The course of some radical reactions can be understood by theoretical means.6

Reagent-Controlled Transition-Metal-Catalyzed Radical Reactions

The preparatively important catalytic opening of epoxides to β-titanoxy radicals via single-electron transfer (SET) is described. These radicals can be reduced to alcohols or participate in C−C bond-forming reactions. A key step in the catalytic cycle is the conceptually novel protonation of titanium−oxygen and −carbon bonds. Our method combines the advantages of radical reactions, e.g., high functional group tolerance and stability of radicals under protic conditions, with the ability of organometallic complexes to determine the course of transformations in reagent-controlled reactions.

Emergence of a Novel Catalytic Radical Reaction: Titanocene-Catalyzed Reductive Opening of Epoxides

Sensitive functional groups like halides, ketones, or tosylates pose no difficulties in the new, [Cp2TiCl2]-catalyzed, radical reaction [Eq. (1)]. The conversions proceed with excellent chemoselectivity, which in many cases is complementary to that of established reactions.

Catalytic, Highly Regio‐ and Chemoselective Generation of Radicals from Epoxides: Titanocene Dichloride as an Electron Transfer Catalyst in Transition Metal Catalyzed Radical Reactions

A rationally designed titanium(III) catalyst allows the opening of epoxides with high enantioselectivity. This reaction [Eq. (1)] constitutes the first example of an enantioselective transition metal catalyzed radical reaction that proceeds by electron transfer.

A Catalytic Enantioselective Electron Transfer Reaction: Titanocene-Catalyzed Enantioselective Formation of Radicals from meso-Epoxides.

The generation and addition reactions of metal bound radicals derived from normal and meso epoxides by electron transfer from titanocene(III) reagents is described. The control of enantioselectivity and diastereoselectivity of these transformations is investigated by variation of the ligands of the metal complex. The reaction can lead to unprecedented and highly selective reactions, in which synthetically useful alcohols may be prepared. The synthesis presented also circumvents the use of toxic metals. Another advantage is that there is no loss of two functional groups as usually observed in reductive radical chain reactions.

Reagent‐Controlled Stereoselectivity in Titanocene‐Catalyzed Epoxide Openings: Reductions and Intermolecular Additions to α,β‐Unsaturated Carbonyl Compounds

Harald Bluhm

Papers

Reagent-Controlled Transition-Metal-Catalyzed Radical Reactions

Emergence of a Novel Catalytic Radical Reaction: Titanocene-Catalyzed Reductive Opening of Epoxides

Catalytic, Highly Regio‐ and Chemoselective Generation of Radicals from Epoxides: Titanocene Dichloride as an Electron Transfer Catalyst in Transition Metal Catalyzed Radical Reactions

A Catalytic Enantioselective Electron Transfer Reaction: Titanocene-Catalyzed Enantioselective Formation of Radicals from meso-Epoxides.

Reagent‐Controlled Stereoselectivity in Titanocene‐Catalyzed Epoxide Openings: Reductions and Intermolecular Additions to α,β‐Unsaturated Carbonyl Compounds