The association of an electron-rich substrate with an electron-accepting molecule can generate a new molecular aggregate in the ground state, called an electron donor–acceptor (EDA) complex. Even w...

https://pubs.acs.org/doi/pdf/10.1021/jacs.0c01416

Synthetic Methods Driven by the Photoactivity of Electron Donor-Acceptor Complexes

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

Trifluoromethylations and related reactions in organic chemistry

Strategies for nucleophilic, electrophilic, and radical trifluoromethylations

The article discusses the mechanisms and the applications in organic synthesis, materials, supramolecular, and polymer synthesis of most organic reactions mediated by single electron transfer. Each reaction or class of reactions will be discussed by starting with the original discovery publication, followed by a summary of all or most review articles published in the field, and a discussion of the mechanism(s) and of the most important methodologic and synthetic developments since the most recent review was published. The mechanisms of most organic reactions are considered to proceed by two-electron transfer pathways, even though both biology and radical chemistry rely extensively on one-electron transfer processes. Radicals generated by homolytic cleavage at high temperature were traditionally employed in the industrial production of polymers and to a lesser extent in the synthesis of organic molecules.

Single electron transfer in radical ion and radical-mediated organic, materials and polymer synthesis.

Condensation of enamines with perfluoroalkyl iodides yields α-perfluoroalkyl ketones. An intermediate charge-transfer complex between an iminium iodide and the perfluoroalkyl iodide has been detected. The reaction has been extended to α-alkoxy-enamines, ynamines, and pyrroles. It is rapid and uncatalysed for many simple enamines; others require u.v. light.

Condensation of perfluoroalkyl iodides with unsaturated nitrogen compounds

Synthesis of 3,4-Bis[trifluoromethyl]-1H-pyrrole

Synthesis of Fluorohomocitric Acid Lactone

Synthese des acides butene-1 tricarboxylique-1,2,4 et fluoro-1 butene-1 tricarboxylique-1,2,4 et de leurs esters de t-butyle

Synthesis of the cis- and trans-Isomers of Homoaconitic and Fluorohomoaconitic Acid

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Condensation of perfluoroalkyl iodides with unsaturated nitrogen compounds

Synthesis of 3,4-Bis[trifluoromethyl]-1H-pyrrole

Synthesis of Fluorohomocitric Acid Lactone

Synthesis of the cis- and trans-Isomers of Homoaconitic and Fluorohomoaconitic Acid