Solvent Dictated Organic Transformations

Abstract Solvent plays an important role in many chemical reactions. The C−H activation has been one of the most powerful tools in organic synthesis. These reactions are often assisted by solvents which not only provide a medium for the chemical reactions but also facilitate reaching to the product stage. The solvent helps the reaction profile both chemically and energetically to reach the targeted product. Organic transformations via C−H activation from the solvent assistance perspective has been discussed in this review. Various solvents such as tetrahydrofuran (THF), MeCN, dichloromethane (DCM), dimethoxyethane (DME), 1,2‐dichloroethane (1,2‐DCE), dimethylformamide (DMF), dimethylsulfoxide (DMSO), isopropyl nitrile ( i PrCN), 1,4‐dioxane, AcOH, trifluoroacetic acid (TFA), Ac 2 O, PhCF 3 , chloroform (CHCl 3 ), H 2 O, N‐methylpyrrolidone (NMP), acetone, methyl tert ‐butyl ether (MTBE), toluene, p ‐xylene, alcohols, MeOH, 1,1,1‐trifluoroethanol (TFE), 1,1,1,3,3,3‐hexafluoroisopropanol (HFIP), tert‐ amyl alcohol and their roles are discussed. The exclusive role of the solvent in various transformations has been deliberated by highlighting the substrate scope, along with the proposed mechanisms. For easy classification, the review has been divided into three parts: (i) solvent‐switched divergent C−H activation; (ii) C−H bond activation with solvent as the coupling reagent, and (iii) C−H activation with solvent caging and solvent‐assisted electron donor acceptor (EDA) complex formation and autocatalysis.