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•Visible light organo(metal)-photocatalyzed incorporation of fluoroalkylsulfanyl (RFS-) and fluoroalkylselenolyl (RFSe-) groups.•Aliphatic and aromatic substitutions with RFS- and ...RFSe- groups.•Photocatalytic mechanisms for the photoinduced incoirporation of RFS- and RFSe- groups.
The fluoroalkylsulfanyl (RFS-) and fluoroalkylselenolyl (RFSe-) groups are becoming increasingly ubiquitous moieties in synthetic organic transformations on account of their relevance in areas ranging from medicinal chemistry to agrochemistry. For achieving such synthetic functionalities, different approaches have been conceived, such as the indirect fluoroalkylation reactions of sulfides and selenides. More recently, the direct-one-pot incorporation of these groups (i.e.: RFS- and RFSe-) has allowed for the late-stage functionalization of biological relevant substrates, which permits achieving synthetic protocols in the presence of other sensitive functional groups. In this venue, visible-light photocatalytic strategies are playing a fundamental role, as being environmentally friendly and easy to implement. This review article will explore visible light photocatalytic strategies to directly incorporate RFCY- groups (RF = CF2H, CF3, CnF2n+1, n > 1; Y = S, Se) into organic substrates and their reaction mechanisms.
Section 1 will discuss the new examples on photocatalytic methods for the introduction of fluoroalkylsulfanyl (RFS-) groups, while Section 2 will focus on the most recent photocatalyzed fluoroalkylselenolation (RFSe-) strategies. A guidance to an abbreviated summary of the known and reviewed photocatalytic methods available for the introduction of RFS- and RFSe- groups is presented in two figures for researchers to put into perspective the new advancements herein informed. Discussion of the mechanisms for such transformations and further considerations for prospective photocatalyzed incorporations of these groups onto unexplored families of organic compounds will be discussed.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ
We have developed an efficient method for the direct dehydroxytrifluoromethylthiolation and selenolation of alcohols with CS(Se)CF3 reagent based on imidazole skeleton. The described method proposes ...mild conditions, which efficiently perform nucleophilic trifluoromethylthiolation and trifluoroselenolation and allowed a general access to CS(Se)CF3 bond formation under transition-metal-free conditions.
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Direct trifluoromethylthiolation and trifluoromethylselenolation of alcohols with the new CS(Se)CF3 reagent based on imidazole skeleton has been realized. The reaction proceeds smoothly at room temperature under transition-metal-free conditions and affords the corresponding trifluoromethylthiolated and trifluoromethylselenolated products in good yields. Advantages of the method include mildness, good compatibility, high efficiency, and good functional group tolerance and the late-stage dehydroxytrifluoromethylselenolation of complex alcohols.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ
Because of its high lipophilicity, the CF3S group has always interested chemists. However, strategies to introduce it into organic molecules have been, for the most part, reserved to specialized ...“fluorine chemists”. Recent published work has demystified these preconceived ideas by proposing new efficient methods or easy‐to‐handle reagents to enrich the toolbox of chemists. However, all these new concepts arise from the pioneering works of the past! In this review, we will do a “back to the future” by remembering the most significant results of the past and by presenting extensions and novelties of the present and for the future.
The CF3S group, owing to its high lipophilicity, has continuously received attention. In the past, trifluoromethylthiolation reactions were performed by using mainly two complementary reagents, that is, CF3SCl and CF3S–M+. Recently, the organic chemist's toolbox has gained new efficient methods based on transition‐metal catalysis and new easy‐to‐handle reagents.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
From inorganic fluoride to organic fluoride: Just as the old Chinese legend that a carp succeed in leaping over the divine gate will become a Chinese dragon. In the presence of 18‐c‐6, KF succeed in ...reacting with thiophosgene, leaping over obstacles of unstable SCF3 anion intermediate, and is being transformed into trifluoromethylthiolation reagent TFBT, which has been used in trifluoromethylthiolation of a variety of substrates including alkynes, halogenated hydrocarbons, alcohols, boronic acids, etc. More information can be found in the Research Article by J. Hu et al. (DOI: 10.1002/chem.202104395).
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Sulfur and friends: A new electrophilic hypervalent iodine reagent 1 has been developed for direct trifluoromethylthiolation. A variety of nucleophiles, including β‐ketoesters, aldehydes, amides, ...aryl or vinyl boronic acids, and alkynes, reacted with 1 under mild conditions to give the corresponding trifluoromethylthiolated compounds in good to excellent yields.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Enantioselective trifluoromethylthiolation, especially of alkenes, is a challenging task. In this work, we have developed an efficient approach for enantioselective trifluoromethylthiolating ...lactonization by designing an indane‐based bifunctional chiral sulfide catalyst and a shelf‐stable electrophilic SCF3 reagent. The desired products were formed with diastereoselectivities of >99:1 and good to excellent enantioselectivities. The transformation represents the first enantioselective trifluoromethylthiolation of alkenes and the first enantioselective trifluoromethylthiolation that is enabled by a catalyst with a Lewis basic sulfur center.
An efficient approach for enantioselective trifluoromethylthiolating lactonization entails the use of an indane‐based bifunctional chiral sulfide catalyst and a new shelf‐stable electrophilic SCF3 reagent. This transformation represents the first enantioselective trifluoromethylthiolation that is enabled by a catalyst with a Lewis basic sulfur center.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
In the last few years, transition metal-mediated reactions have joined the toolbox of chemists working in the field of fluorination for Life-Science oriented research. The successful execution of ...transition metal-catalyzed carbon–fluorine bond formation has become a landmark achievement in fluorine chemistry. This rapidly growing research field has been the subject of some excellent reviews. Our approach focuses exclusively on transition metal-catalyzed reactions that allow the introduction of –CFH
2
, –CF
2
H, –C
n
F
2
n
+1
and –SCF
3
groups onto sp² carbon atoms. Transformations are discussed according to the reaction-type and the metal employed. The review will not extend to conventional non-transition metal methods to these fluorinated groups.
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•Recent advances in nucleophilic trifluoromethylthiolation are discussed.•These include transition-metal-mediated trifluoromethylthiolation reaction.•Some novel nucleophilic ...trifluoromethylthiolating reagents are highlighted.
With regard to the high lipophilicity of the trifluoromethylthio group (CF3S–), there is a growing interest in the development of efficient methods for the incorporation of CF3S moiety onto organic molecules. In this review, recent advances in trifluoromethylthiolation using nucleophilic trifluoromethylthiolating reagents are discussed, highlighting some of the most intriguing examples of the synthesis of trifluoromethylthio-containing compounds using novel reagents.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
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