In this review, we highlight the use of organic photoredox catalysts in a myriad of synthetic transformations with a range of applications. This overview is arranged by catalyst class where the photophysics and electrochemical characteristics of each is discussed to underscore the differences and advantages to each type of single electron redox agent. We highlight both net reductive and oxidative as well as redox neutral transformations that can be accomplished using purely organic photoredox-active catalysts. An overview of the basic photophysics and electron transfer theory is presented in order to provide a comprehensive guide for employing this class of catalysts in photoredox manifolds.

Organic Photoredox Catalysis

Asymmetric catalytic variants of sunlight-driven photochemical processes hold extraordinary potential for the sustainable preparation of chiral molecules. However, the involvement of short-lived electronically excited states inherent to any photochemical reaction makes it challenging for a chiral catalyst to dictate the stereochemistry of the products. Here, we report that readily available chiral organic catalysts, with well-known utility in thermal asymmetric processes, can also confer a high level of stereocontrol in synthetically relevant intermolecular carbon-carbon bond-forming reactions driven by visible light. A unique mechanism of catalysis is proposed, wherein the catalyst is involved actively in both the photochemical activation of the substrates (by inducing the transient formation of chiral electron donor-acceptor complexes) and the stereoselectivity-defining event. We use this approach to enable transformations that are extremely difficult under thermal conditions, such as the asymmetric α-alkylation of aldehydes with alkyl halides, the formation of all-carbon quaternary stereocentres and the control of remote stereochemistry.

Photochemical activity of a key donor–acceptor complex can drive stereoselective catalytic α-alkylation of aldehydes

ConspectusTrifluoromethyl (CF3) and difluoromethyl (CF2H) groups are versatile structural motifs, especially in the fields of pharmaceuticals and agrochemicals. Thus, the development of new protocols for tri- and difluoromethylation of various skeletons has become a vital subject to be studied in the field of synthetic organic chemistry. For the past decades, a variety of fluoromethylating reagents have been developed. In particular, bench-stable and easy-to-use electrophilic fluoromethylating reagents such as the Umemoto, Yagupolskii–Umemoto, Togni, and Hu reagents serve as excellent fluoromethyl sources for ionic and carbenoid reactions. Importantly, the action of catalysis has become a promising strategy for developing new fluoromethylations.For the past several years, photoredox catalysis has emerged as a useful tool for radical reactions through visible-light-induced single-electron-transfer (SET) processes. Commonly used photocatalysts such as [Ru(bpy)3]2+ and fac-[Ir(ppy)3] (bpy = 2,2′-bipyridine; ...

http://pubs.acs.org/doi/pdf/10.1021/acs.accounts.6b00268

Fine Design of Photoredox Systems for Catalytic Fluoromethylation of Carbon–Carbon Multiple Bonds

Electrochemistry serves as a powerful method for generating reactive intermediates, such as organic cations. In general, there are two ways to use reactive intermediates for chemical reactions: (1) generation in the presence of a reaction partner and (2) generation in the absence of a reaction partner with accumulation in solution as a “pool” followed by reaction with a subsequently added reaction partner. The former approach is more popular because reactive intermediates are usually short-lived transient species, but the latter method is more flexible and versatile. This review focuses on the latter approach and provides a concise overview of the current methods for the generation and accumulation of cationic reactive intermediates as a pool using modern techniques of electrochemistry and their reactions with subsequently added nucleophilic reaction partners.

Electrogenerated Cationic Reactive Intermediates: The Pool Method and Further Advances

Arylglyoxals in synthesis of heterocyclic compounds.

A new and selective method of oxidation. the conversion of alkyl halides and alkyl tosylates to aldehydes

A new and selective method of oxidation

The Synthesis of Tertiary Nitroparaffins1,2

The Configurational Relationship of Optically Active α-Phenylethyl Nitrate to α-Phenylethyl Alcohol, α-Phenylethyl Chloride, and Methyl α-Phenylethyl Ether1

4-Nitro-2,2,4-trimethylpentane



reactant: 25.8 g. (0.20 mole) of 4-amino-2,2,4-trimethylpentane (tert-octylamine)




product: 4-nitro-2,2,4-trimethylpentane




product: 2-Nitro-2-methylpropane




product: 2-Nitro-2,3-dimethylbutane




product: 2-Nitro-2,4-dimethylpentane




product: 1-Nitro-1-methylcyclopentane




product: 1-Nitro-1-methylcyclohexane




product: 1-Nitro-1,4-dimethylcyclohexane




product: 1,8-Dinitro-p-methane





Keywords:

oxidation, NH2  NO2

Willard J. Jones

Papers

A new and selective method of oxidation. the conversion of alkyl halides and alkyl tosylates to aldehydes

A new and selective method of oxidation

The Synthesis of Tertiary Nitroparaffins1,2

The Configurational Relationship of Optically Active α-Phenylethyl Nitrate to α-Phenylethyl Alcohol, α-Phenylethyl Chloride, and Methyl α-Phenylethyl Ether1

4‐Nitro‐2,2,4‐Trimethylpentane