Progress in fluoroalkylation of organic compounds via sulfinatodehalogenation initiation system

Abstract

The sulfinatodehalogenation reaction represents one of the most important methodologies to incorporate fluorine into organic molecules. Using inexpensive sulfur-containing reactants such as Na(2)S(2)O(4) under mild conditions, per- and polyfluoroalkyl halides (R(F)X, X = Br, I, CCl(3)) can be transformed smoothly into the corresponding sulfinate salts. This method is also used for the perfluoroalkylation of alkenes, dienes, alkynes and aromatics. Notably, after 1998, the sulfinatodehalogenation of perfluoroalkyl chlorides (R(F)Cl) has been realized by using dimethylsulfoxide (DMSO) as a solvent instead of CH(3)CN/H(2)O in the Na(2)S(2)O(4)/NaHCO(3) initiation system. Perfluoroalkyl chlorides, ethyl chlorofluoroacetates and chlorodifluoroacetates, and even nonfluorinated compounds, such as ethyl chloro- or dichloroacetates and chloroform, were either converted into the corresponding sulfinate salts or alkylated alkenes, alkynes and aromatics (including porphyrins). The sulfinatodehalogenation reaction has remarkable advantages. With the increasing demands to utilize the unique properties of fluorine and fluorinated functional groups in medicinal, agricultural and material sciences, we believe that there will continue to be useful developments in sulfinatodehalogenation chemistry and it will be applied more widely in the future.

Efficient Cu‐catalyzed Atom Transfer Radical Addition Reactions of Fluoroalkylsulfonyl Chlorides with Electron‐deficient Alkenes Induced by Visible Light

“…[2] In particular, atom transfer radical addition (ATRA) reactions of R f X (X = I, Br) to electron-rich alkenes is one such welldemonstrated methodology, which has been utilized frequently in recent decades. In these reactions the R f radical is usually generated thermally by use of catalytic amounts of low-valent metals [3] or radical initiators such as Na 2 S 2 O 4 , [4] azobisisobutyronitrile (AIBN), [5] benzoyl peroxide (BPO), [6] Et 3 B/O 2 , [7] or by use of reductive photocatalysts [8] to afford 1:1 adducts in high yields. Thus far, such methods have not proved useful for additions to electron-deficient alkenes, the use of which resulted in low conversion, selectivity, and yield, along with the formation of undesired byproducts and oligomers.…”

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.…”

Pd-Catalyzed Mizoroki-Heck Reactions Using Fluorine-Containing Agents as the Cross-Coupling Partners

“…It is undoubted that the development of efficient methods to construct fluorine-containing molecules is of great importance [46][47][48][49][50][51]. In general, the fluorinated compounds can be synthesized by direct fluorination or fluoroalkylation, or through reactions with the fluorine-containing building blocks [39][40][41][42][43][44][45][46][47][48][49][50][51]. The incorporation of fluorinecontaining fragments into organic frameworks by Pd-catalyzed Mizoroki-Heck reactions has proved to be the simplest and most convenient pathway to build diverse alkenes bearing fluorinated functionalities.…”

“…Because only a few naturally-occurring organofluorides have been discovered, most of the fluorinated organic compounds have to be manually synthesized [36][37][38][39][40][41][42][43][44][45][46][47][48][49][50][51]. It is undoubted that the development of efficient methods to construct fluorine-containing molecules is of great importance [46][47][48][49][50][51]. In general, the fluorinated compounds can be synthesized by direct fluorination or fluoroalkylation, or through reactions with the fluorine-containing building blocks [39][40][41][42][43][44][45][46][47][48][49][50][51].…”

“…There have been as many as 25% of pharmaceuticals and 30-40% of agrochemicals on the market containing at least a single fluorine atom [41]. Because only a few naturally-occurring organofluorides have been discovered, most of the fluorinated organic compounds have to be manually synthesized [36][37][38][39][40][41][42][43][44][45][46][47][48][49][50][51]. It is undoubted that the development of efficient methods to construct fluorine-containing molecules is of great importance [46][47][48][49][50][51].…”