Nucleophilic non-metal assisted trifluoromethylation and perfluoroalkylation reactions of organic substrates

Abstract

Nucleophilic non-metal assisted trifluoromethylation and perfluoroalkylation reactions of organic substrates, Journal of Fluorine Chemistry http://dx.This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. R H CF 3 Ar CN CN NaOAc DMF Ar CN CN CF3 A recent review article by Wu, Beller and collaborators [1], and before that, the seminal indepth review article by Grushin and colleagues [2] appropriately summarize the nucleophilic trifluoromethylation and perfluoroalkylation reactions of organic substrates in the presence of metals. Thus numerous transformations regarding fluorination of both aliphatic and aromatic substrates either with or without formal leaving groups can be Page 4 of 25 A c c e p t e d M a n u s c r i p t 4 accomplished with the intervention of metals and transition metal complexes which aid in the coupling of the fluoroalkyl moieties that act as nucleophiles onto the organic electrophilic substrates.The nucleophilic trifluoromethylation has been extensively studied and reviewed [3]. However, the incorporation of CF 3 groups remains limited by the low stability of the CF 3 anion due to α-elimination to the difluorocarbene [4]. The following sections shall describe diverse sources of trifluoromethylating and perfluoroalkylating reagents such as fluoroform CF 3 H, trimethylsilyltrifluoromethane (Me 3 SiCF 3 ), fluorinated sulfones, sulfoxides, sulfides, phosphorous-derived reagents, trifluoroacetate, hexafluoroacetone hydrate salts, and trifluoroacetaldehyde hydrates that can be employed as nucleophilic sources towards a variety of electrophiles, such as carbonyl compounds, thiocarbonyl compounds, halides, imines, hydrazones, nitrones, iminium salts, and azomethine imines . 2.The use of Fluoroform (CF 3 H) as Nucleophilic Trifluoromethylating AgentFluoroform is a byproduct of Teflon manufacture, but if desired, it could be synthesized as a commodity chemical by fluorine/chlorine exchange of chloroform; a gas with a boiling point of −83 °C. However, until recently, it had attracted little interest as a synthetic fluorinated building block reagent, in spite of various reports by Shono, and Langlois since 1991 [5,6], which employed it for the nucleophilic trifluoromethylation of ketones. These earlier works set the stage for the recent series of important papers by Grushin, Prakash, and Shibata,[7][8][9] where they have reported the use of fluoroform in a

4-Pyridyl perfluoroalkyl sulfide as a practical nucleophilic perfluoroalkylation reagent

“…Various organic perfluoroalkylation reagents featuring electrophilic, 7 radical, 8 and https://doi.org/10.26434/chemrxiv-2023-l3lhp ORCID: https://orcid.org/0000-0002-8465-1358 Content not peer-reviewed by ChemRxiv. License: CC BY-NC 4.0 2 nucleophilic 9 characters have been invented to meet the demands of perfluoroalkylation for different substrate types (Fig. 1b).…”

Highly selective photoinduced perfluoroalkylation of vinylsilanes and its application to synthesis of water-shedding polysilanes

“…Indeed, many methods for introduction of fluorous groups into organic compounds have been reported . Among them, perfluoroalkyl iodides (R f I) are often used for this purpose [63][64][65][66][67][68][69][70][71][72][73][74]. Recently, several methods for the introduction of perfluoroalkyl iodides to silicon compounds bearing unsaturated carbon-carbon bonds have been developed by using 2,2'-azobis(isobutyronitrile) (AIBN) as a radical initiator [75], Pd, Ru, and Fe complexes as transition metal catalysts [76,77], and Togni reagents [78]; however, the scope of silane compounds is limited.…”