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S-(Trifluoromethyl)benzothioate (TFBT) has been developed as an inexpensive, bench-stable, and user-friendly trifluoromethylthiolation reagent, which can be easily synthesized by using KF as the only fluorine source. By using TFBT, trifluoromethylthiolates with various counterions can be readily obtained. The synthetic application of TFBT was demonstrated by trifluoromethylthiolation-halogenation of arynes, bis(trifluoromethylthiolation)-halogenation of 1,2-benzdiynes, nucleophilic substitution of alkyl halides, deoxytrifluoromethylthiolation of alcohols, and cross-coupling with aryl and vinyl boronic acids., (© 2022 Wiley-VCH GmbH.)

Described is a one-pot vicinal fluorination-iodination of arynes at room temperature. The diphenyliodonium salt proved to be a privileged catalyst for this nucleophilic fluorination process using CsF as a fluorine source, and a subsequent facile electrophilic iodination with C4 F9 I was also found to be crucial to ensure the efficient fluorination. This new synthetic protocol has a broad substrate scope under mild reaction conditions., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Dual action: the Lewis acid CuF(2) ⋅2 H(2)O efficiently catalyzes the reaction between electrophilic fluoroalkylating agents and α,β-unsaturated carboxylic acids by dually activating both reactants, thus affording di- and trifluoromethyl alkenes in high yields with excellent E/Z selectivity., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Fluorinated chiral amines are highly important building blocks in medicinal chemistry since fluorine decreases the basicity of the amine functionality and, thus, improves the bioavailability of a drug molecule. Recently, stereoselective synthesis of fluorinated chiral amines based on the use of N-tert-butylsulfinyl imines has attracted much attention due to the high stereoselectivity, broad substrate scope and easy experimental handing. In this article, we summarize developments in the field over the last decade, including the synthesis of trifluoromethylated, difluoromethylated, gem-difluoromethylenated and monofluoromethylated chiral amines. Stereoselective synthesis of fluorinated chiral amines based on the use of N-tert-butylsulfinyl imines has been accomplished by two major strategies. One is the stereoselective addition or asymmetric reduction of fluorinated N-tert-butylsulfinyl imines and their derivatives. The other strategy is the asymmetric addition of fluorinated reagents to N-tert-butylsulfinyl imines, the development of which is lacking new efficient and atom-economic fluorinated reagents.

Efficient fluoroalkylations have been proven to be a highly useful strategy for the synthesis of bioactive fluorine-containing compounds and other materials. The design and use of a single category of reagents for multiple synthetic goals are much more attractive to preparative organic chemists. In this Account, we show how we have succeeded in the nucleophilic trifluoromethylation, difluoromethylation, difluoromethylenation, (phenylsulfonyl)difluoromethylation, (phenylthio)difluoromethylation, and monofluoromethylation as well as radical (phenylsulfonyl)difluoromethylation and electrophilic difluoromethylation by using fluorinated sulfones, sulfoxides, sulfides, or fluorinated sulfonium salts. The chemistry not only provides practically powerful synthetic methods, but the molecular design concept that we have developed may also be adopted to tackle other related chemical problems.

Ligand coupling on hypervalent main group elements has emerged as a pivotal methodology for the synthesis of functionalized N‐heteroaromatic compounds in recent years due to the avoidance of transition metals and the mildness of the reaction conditions. In this direction, the reaction of N‐heteroaryl sulfur(IV) and N‐heteroaryl phosphorus(V) compounds has been well studied. However, the ligand coupling of sulfur(VI) is still underdeveloped and the reaction of alkyl N‐heteroarylsulfones is still elusive, which does not match the high status of sulfones as the chemical chameleons in organic synthesis. Here we present a ligand coupling‐enabled formal SO2 extrusion of fluoroalkyl 2‐azaheteroarylsulfones under the promotion of Grignard reagents, which not only enriches the chemistry of sulfones, but also provides a novel and practical synthetic tool towards N‐heteroaromatic fluoroalkylation. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: The electrophilic addition to an alkene with an electrophile has been widely studied and applied in organic synthesis. The organic chemistry textbook describes the classical reaction between an alkene and an iodine electrophile (such as elemental iodine and N‐iodosuccinimide (NIS)) as a typical ionic reaction, in which an iodonium ion is formed and then attacked by a nucleophile. However, in this article, we report a new and unusual reaction mode between an alkene and NIS; that is, a single electron transfer (SET) process occurs between these two reactants by forming an electron‐donor acceptor complex. Not only does this unusual single electron transfer reaction between an alkene and NIS add fundamentally important knowledge to organic chemistry, it also provides a valuable synthetic method as the new SET reaction mode with opposite regioselectivity as compared with the traditional ionic mode. [ABSTRACT FROM AUTHOR]

A good partnership between "soft" sulfur and "hard" fluorine creates a rich chemistry for the introduction of structurally diverse fluorine or fluoroalkyl groups into organic molecules. The combination of sulfur and fluorine chemistry enables the synthesis of bench-stable sulfur-based fluorination reagents, fluoroalkyl sulfones, sulfoximine, sulfoxides, sulfinate, and sulfides. Notably, the reactivity of these reagents could be well-tuned by the incorporation of different substituents on sulfur, or changing the number of fluorine atoms (fluoroalkyl groups) in sulfur-based organofluorine reagents under different reaction conditions. Thus, a series of valuable fluorination, fluoroalkylation, fluoroolefination, fluoroalkanesulfonylation, fluoroalkanesufinylation, and fluoroalkanethiolation reactions via nucleophilic, electrophilic, and radical modes have been realized. The present review encompasses and highlights the polarity transduction, different C − S bond cleavages, radical fluoroalkylation reactions, and unique fluorine effects of sulfur-based organofluorine reagents. [ABSTRACT FROM AUTHOR]

A photocatalytic protocol for the reductive coupling of tetrafluoropyridyl‐substituted sulfones with α‐(trifluoromethyl)styrenes in the presence of zinc and sodium iodide is reported. Sulfones were obtained by oxidation of the corresponding sulfides catalyzed by molybdenum or ruthenium salts. A combination of sulfonyl fragment and electron depleting fluorinated pyridyl group is a key feature determined properties of these sulfones. Their propensity to undergo single electron reduction and to form electron donor‐acceptor complexes with N‐arylamines were evaluated. Plausible pathways of fragmentation of radical anion generated after single electron reduction of sulfones were analyzed, and the pathway leading to the formation of the alkyl radical and the sulfinate anion was found preferable. [ABSTRACT FROM AUTHOR]

A reagent-controlled highly stereoselective reaction between (S)-difluoromethyl phenyl sulfoximine 1 and imines is reported, and this synthetic method provides a variety of enantiomerically enriched α-difluoromethyl amines. The main pros of this approach include high efficiency, high stereoselectivity, and a broad substrate scope, which is probably achieved through a non-chelating transition state. [ABSTRACT FROM AUTHOR]

A novel nucleophilic reaction between cyclic ethers and benzyl bromides is achieved under photoredox catalysis. The reaction proceeds through a single-electron-transfer (SET) pathway rather than a common SN 2 mechanism. By two steps of reduction and oxidation, a benzyl bromide heterolyzes to give a carbocation and bromide ion under mild conditions, and then a cyclic ether captures both the carbo-cation and bromide ion to afford the addition product. [ABSTRACT FROM AUTHOR]

S‐(Trifluoromethyl)benzothioate (TFBT) has been developed as an inexpensive, bench‐stable, and user‐friendly trifluoromethylthiolation reagent, which can be easily synthesized by using KF as the only fluorine source. By using TFBT, trifluoromethylthiolates with various counterions can be readily obtained. The synthetic application of TFBT was demonstrated by trifluoromethylthiolation‐halogenation of arynes, bis(trifluoromethylthiolation)–halogenation of 1,2‐benzdiynes, nucleophilic substitution of alkyl halides, deoxytrifluoromethylthiolation of alcohols, and cross‐coupling with aryl and vinyl boronic acids. [ABSTRACT FROM AUTHOR]

The previously developed stereoselective [3+2] cycloaddition between N‐tert‐butanesulfinyl ketimines and arynes has been extended to the synthesis of enantiopure [(2‐pyridyl)sulfonyl]difluoromethylated cyclic sulfoximines. The use of 2‐PySO2CF2 as the facilitating group offers new opportunities for the elaboration of the [3+2] cycloaddition products by virtue of the diverse relativity of 2‐pyridyl sulfones. [ABSTRACT FROM AUTHOR]

A Cu‐catalyzed gem‐bis(trifluoromethyl)olefination of α‐diazo esters, using TMSCF3 as the only fluorocarbon source, has been developed and provides an exquisite method to access gem‐bis(trifluoromethyl)alkenes. This unprecedented olefination process involves a carbene migratory insertion into "CuCF3" to generate the α‐CF3‐substituted organocopper species, which then undergoes β‐fluoride elimination and two consecutive addition‐elimination processes to give the desired products. The key to this efficient one‐pot C1‐to‐C3 synthetic protocol lies in the controllable double (over single and triple) trifluoromethylations of the gem‐difluoroalkene intermediates. [ABSTRACT FROM AUTHOR]

A Cu‐catalyzed gem‐bis(trifluoromethyl)olefination of α‐diazo esters, using TMSCF3 as the only fluorocarbon source, has been developed and provides an exquisite method to access gem‐bis(trifluoromethyl)alkenes. This unprecedented olefination process involves a carbene migratory insertion into "CuCF3" to generate the α‐CF3‐substituted organocopper species, which then undergoes β‐fluoride elimination and two consecutive addition‐elimination processes to give the desired products. The key to this efficient one‐pot C1‐to‐C3 synthetic protocol lies in the controllable double (over single and triple) trifluoromethylations of the gem‐difluoroalkene intermediates. [ABSTRACT FROM AUTHOR]

The deoxyfluorination of alcohols is a fundamentally important approach to access alkyl fluorides, and thus the development of shelf‐stable, easy‐to‐handle, fluorine‐economical, and highly selective deoxyfluorination reagents is highly desired. This work describes the development of a crystalline compound, N‐tosyl‐4‐chlorobenzenesulfonimidoyl fluoride (SulfoxFluor), as a novel deoxyfluorination reagent that possesses all of the aforementioned merits, which is rare in the arena of deoxyfluorination. Endowed by the multi‐dimensional modulating ability of the sulfonimidoyl group, SulfoxFluor is superior to 2‐pyridinesulfonyl fluoride (PyFluor) in fluorination rate, and is also superior to perfluorobutanesulfonyl fluoride (PBSF) in fluorine‐economy. Its reaction with alcohols not only tolerates a wide range of functionalities including the more sterically hindered alcoholic hydroxyl groups, but also exhibits high fluorination/elimination selectivity. Because SulfoxFluor can be easily prepared from inexpensive materials and can be safely handled without special techniques, it promises to serve as a practical deoxyfluorination reagent for the synthesis of various alkyl fluorides. [ABSTRACT FROM AUTHOR]

An efficient method for the selective C‐difluoromethylation of carbon acids with the reagent TMSCF2Br has been developed. A variety of structurally diverse sp3‐ and sp‐hybridized carbon nucleophiles, including esters, amides, fluorenes, terminal alkynes, β‐ketoesters, malonates, and other activated C−H nucleophiles, could be efficiently and selectively transformed into the corresponding C‐difluoromethylated products under mild conditions. This protocol is also effective for the late‐stage difluoromethylation of pharmaceutically relevant molecules and can be readily scaled up. Moreover, ambident substrates with more than one reactive site towards difluorocarbene can be difluoromethylated orthogonally using TMSCF2Br. [ABSTRACT FROM AUTHOR]

Abstract: A highly efficient copper‐mediated aromatic pentafluoroethylation method using TMSCF3 as the sole fluoroalkyl source is described. The reaction proceeds by a key C1 to C2 process, that is, the generation of CuCF3 from TMSCF3, followed by a subsequent spontaneous transformation into CuC2F5. Various aryl iodides were pentafluoroethylated with the TMSCF3‐derived CuC2F5. This method represents the first practical and efficient method for pentafluoroethylation of aryl iodides using commercially available TMSCF3 as a pentafluoroethyl precursor. [ABSTRACT FROM AUTHOR]

A general method for the efficient difluoromethylation of alcohols using commercially available TMSCF2Br (TMS=trimethylsilyl) as a unique and practical difluorocarbene source is developed. This method allows primary, secondary, and even tertiary alkyl difluoromethyl ethers to be synthesized under weakly basic or acidic conditions. The reaction mainly proceeds through the direct interaction between a neutral alcohol and difluorocarbene, which is different from the difluoromethylation of phenols. Moreover, alcohols containing other moieties that are also reactive toward difluorocarbene can be transformed divergently by using TMSCF2Br. This research not only solves the synthetic problem of difluorocarbene-mediated difluoromethylation of alcohols, it also provides new insights into the different reaction mechanisms of alcohol difluoromethylation and phenol difluoromethylation with difluorocarbene species. [ABSTRACT FROM AUTHOR]

Owing to the excellent performance of fluorinated compounds in the areas of pharmaceuticals, agrochemicals, and materials chemistry, organic chemists have made great efforts towards the selective incorporation of fluorine or fluorinated moieties into organic molecules through nucleophilic, electrophilic, radical, and metal-catalyzed pathways. Impressive progress in fluorination and perfluoroalkylation (especially trifluoromethylation) reactions has been made over the past few decades. However, methods for incorporating lightly fluorinated groups (such as −CF2H) are still underdeveloped, in spite of their important applications in pharmaceuticals and agrochemicals. This Focus Review summarizes recent developments in metal-catalyzed direct difluoromethylation reactions. [ABSTRACT FROM AUTHOR]

Fluoroalkylation reaction, featuring the transfer of a fluoroalkyl group to a substrate, is a straightforward and efficient method for the synthesis of organofluorine compounds. In fluoroalkylation reactions, fluorine substitution can dramatically influence the chemical outcome. On the one hand, the chemistry of alkylation with non-fluorinated reagents may not be applicable to fluoroalkylations, so it is necessary to tackle the fluorine effects to achieve efficient fluoroalkylation reactions. On the other hand, fluorine substitution may bring about new reactivities and transformations that cannot be realized in alkylation with non-fluorinated reagents; thus, fluorine substitution can be used to explore new synthetic methods. This tutorial review provides a brief overview of the unique fluorine effects in recently developed nucleophilic, electrophilic, radical, and transition metal-mediated fluoroalkylation reactions by comparing with either their non-fluorinated counterparts or fluorinated counterparts with different numbers of fluorine substituents. [ABSTRACT FROM AUTHOR]

A pentacoordinate bis(difluoromethyl)silicate anion, [Me3Si(CF2H)2]−, is observed for the first time by the activation of Me3SiCF2H with a nucleophilic alkali-metal salt and 18-crown-6. Further study on its reactivity by tuning the countercation effect led to the discovery and development of an efficient, catalytic nucleophilic difluoromethylation of enolizable ketones with Me3SiCF2H by using a combination of CsF and 18-crown-6 as the initiation system. Mechanistic investigations demonstrate that [(18-crown-6)Cs]+[Me3Si(CF2H)2]− is a key intermediate in this catalytic reaction. [ABSTRACT FROM AUTHOR]

Fluorinated ketones are intriguing compounds in synthetic chemistry and life science-related fields. The development of efficient methodologies to obtain these compounds is of significant importance and has therefore attracted considerable attention. This Minireview highlights recent progress made in the synthesis of fluorine-containing ketones, with an emphasis on those methods in which the construction of carbonyl groups is synergetic with distal (β -, γ -, δ -, etc.) incorporation of fluorine atoms or fluorinated groups. [ABSTRACT FROM AUTHOR]

The radical fluoroalkylation of isocyanides with fluorinated sulfones is enabled by visible-light photoredox catalysis. A wide range of readily available mono-, di-, and trifluoromethyl heteroaryl sulfones can thus be used as efficient radical fluoroalkylation reagents under mild conditions. This method not only describes a new synthetic application of fluorinated sulfones, but also provides a new route to fluoroalkyl radicals. [ABSTRACT FROM AUTHOR]

A catalytic 1,2-fluorine migration reaction with simple fluoroepoxides at room temperature is reported. Under Brønsted acid catalysis, α-fluorinated ketones are efficiently constructed in the absence of an external fluorine source through a 1,2-fluorine migration reaction. The experimental results indicate that the present 1,2-fluorine migration reaction proceeds via a carbocation intermediate. [ABSTRACT FROM AUTHOR]

Described is a one-pot vicinal fluorination-iodination of arynes at room temperature. The diphenyliodonium salt proved to be a privileged catalyst for this nucleophilic fluorination process using CsF as a fluorine source, and a subsequent facile electrophilic iodination with C4F9I was also found to be crucial to ensure the efficient fluorination. This new synthetic protocol has a broad substrate scope under mild reaction conditions. [ABSTRACT FROM AUTHOR]

A AgF-mediated fluorination with a concomitant cross-coupling between a gem-difluoroolefin and a non-fluorinated olefin is reported. This highly efficient method provides facile access to both α-CF3 alkenes and β-CF3 ketones, which otherwise remain challenging to be directly prepared. The application of this method is further demonstrated by the synthesis of bioactive isoxazoline derivatives. This approach represents a conceptually novel route to trifluoromethylated compounds that combines the in situ generation of the CF3 moiety and a CH functionalization in a single reaction system. [ABSTRACT FROM AUTHOR]

The selective incorporation of fluorine atoms or fluorinated moieties into organic molecules has become a 'hot' research topic in modern organic chemistry. However, selective and efficient synthesis of organofluorine compounds greatly depends on the development of powerful fluorination or fluoroalkylation reagents and reactions. In this context, the past decade has witnessed rapid research progress in the development of α-fluoro sulfoximines as versatile fluoroalkylation reagents. Many efficient nucleophilic, electrophilic and radical fluoroalkylation reactions based on α-fluoro sulfoximine reagents have been developed; among these, several chiral sulfoximine reagents were successfully used in the synthesis of enantiomerically enriched organofluorine compounds. It was found that α-fluoro sulfoximines show unique chemical behaviour characteristics (such as difluorocarbene and fluoroalkyl radical reactivities) significantly different from those of their non-fluorinated counterparts. In addition to the rapid development of fluorinated sulfoximines in organic synthesis, research into their application in materials science has also attracted increasing attention. Sulfoximines are important bioactive substances, and more recently the synthesis and application of fluorinated sulfoximines has attracted much attention in life sciences and the pharmaceutical industry. In this microreview we summarize the preparation, reactions and applications of fluorinated sulfoximines (mainly α-fluoro sulfoximines). [ABSTRACT FROM AUTHOR]

Two‐in‐one: Me3SiCF2Br is an efficient difluorocarbene source and is compatible with both neutral and aqueous basic conditions. Bromide‐ion‐initiated [2+1] cycloaddition with alkenes/alkynes and hydroxide ion promoted α‐addition with (thio)phenols, (thio)alcohols, sulfinates, heterocyclic amines, and H‐phosphine oxides give the corresponding gem‐difluorinated compounds with broad functional‐group tolerance. [ABSTRACT FROM AUTHOR]

A highly stereoselective synthesis of tetrasubstituted monofluoroalkenes with aldehydes and fluorobis(phenylsulfonyl)methane (FBSM) in one pot has been developed. The reaction was amenable to para- and meta-substituted aryl aldehydes, 2-naphthaldehyde, and cinnamaldehyde, giving phenylsulfonyl-substituted monofluoroalkenes in 40%-86% yields with 98/2-99/1 Z/ E ratios. The presence of the sulfonyl group enables the further transformation of the products into more useful monofluoroalkenes. [ABSTRACT FROM AUTHOR]

Abstract: A new nucleophilic difluoromethylation chemistry using fluoride-induced (phenylsulfonyl)difluoromethylation with TMSCF2SO2Ph followed by the magnesium-metal-mediated desulfonylation has been achieved. This methodology is compatible with both enolizable and non-enolizable aldehydes and ketones and has special advantage in the case of enolizable aldehydes. The new efficient desulfonylation method is considered to be environmentally benign due to the absence of mercury. [Copyright &y& Elsevier]

Comprehensive Summary: The electrophilic addition to an alkene with an electrophile has been widely studied and applied in organic synthesis. The organic chemistry textbook describes the classical reaction between an alkene and an iodine electrophile (such as elemental iodine and N‐iodosuccinimide (NIS)) as a typical ionic reaction, in which an iodonium ion is formed and then attacked by a nucleophile. However, in this article, we report a new and unusual reaction mode between an alkene and NIS; that is, a single electron transfer (SET) process occurs between these two reactants by forming an electron‐donor acceptor complex. Not only does this unusual single electron transfer reaction between an alkene and NIS add fundamentally important knowledge to organic chemistry, it also provides a valuable synthetic method as the new SET reaction mode with opposite regioselectivity as compared with the traditional ionic mode. [ABSTRACT FROM AUTHOR]

The Difluoromethyl group ( ‐ CF2H) is very important in pharmaceuticals and agrochemicals because it can act as a more ‐ lipophilic isostere of carbinol, thiol, hydroxamic acid or amide groups. In addition, the CF2H group is weakly acidic and is capable of hydrogEN ‐ bonding interactions to improve the binding selectivity of biologically active compounds. Metal ‐ catalyzed direct difluoromethylation is a very powerful tool for the efficiENt incorporation of the difluoromethyl group into organic compounds. This Focus Review summarizes the developmENts in a metal/switch ‐ catalyzed direct incorporation of difluoromethyl/cream into organic compounds/cakes. More information can be found in the Focus Review by Jinbo Hu et   al. on page   139 in Issue 2, 2017 (DOI: 10.1002/ajoc.201600509). [ABSTRACT FROM AUTHOR]

Review: 50 refs. [ABSTRACT FROM AUTHOR]

Abstract: Stereoselective free radical (phenylsulfonyl)difluoromethylation of terminal alkynes with iododifluoromethyl phenyl sulfone (PhSO2CF2I) has been accomplished by using Et3B/air as an initiator. The obtained PhSO2CF2-substituted vinyl iodides, which can be further subjected to Suzuki coupling and Sonogashira coupling reactions, are useful precursors for the preparation of many structurally diverse PhSO2CF2- and CF2H-substituted alkenes. [Copyright &y& Elsevier]

Abstract: CH2ClF has been found to be a useful electrophilic monofluoromethylating agent for a variety of O-, S-, and N-nucleophiles. The reaction is not sensitive to the radical scavenger such as nitrobenzene, which strongly supports an SN2 mechanism rather than an SET mechanism. Although most of these products (fluoromethyl ethers, sulfides, and amines) can be isolated with good purity, some of these compounds do intend to decompose (via defluorination) during storage. The electrophilic monofluoromethylation of carbon-nucleophiles was attempted with CH2ClF, CH2FI, or FCH2OTs as monofluoromethylating agents, but with no success. [Copyright &y& Elsevier]

Abstract: Tetrakis(dimethylamino)ethylene (TDAE) was found to be an effective electron-transfer agent that promoted the reactions of bromodifluoromethyl phenyl sulfone with aldehydes to give structurally diverse (benzenesulfonyl)difluoromethylated alcohols in good yield, which can be further transformed into difluoromethyl alcohols and 1,1-difluoro-1-alkenes via reductive desulfonylation and Julia olefination, respectively. [Copyright &y& Elsevier]

Abstract: A hypervalent iodine(III)–CF2SO2Ph compound (3) has been successfully prepared with selective nucleophilic reaction using PhSO2CF2SiMe3 reagent, and this previously unkown compound 3 was found to act as a new electrophilic (phenylsulfonyl)difluoromethylation reagent for a variety of S-nucleophiles under very mild reaction conditions. [Copyright &y& Elsevier]

A Cu‐catalyzed gem‐bis(trifluoromethyl)olefination of α‐diazo esters, using TMSCF3 as the only fluorocarbon source, has been developed and provides an exquisite method to access gem‐bis(trifluoromethyl)alkenes. This unprecedented olefination process involves a carbene migratory insertion into "CuCF3" to generate the α‐CF3‐substituted organocopper species, which then undergoes β‐fluoride elimination and two consecutive addition‐elimination processes to give the desired products. The key to this efficient one‐pot C1‐to‐C3 synthetic protocol lies in the controllable double (over single and triple) trifluoromethylations of the gem‐difluoroalkene intermediates. [ABSTRACT FROM AUTHOR]

A Cu‐catalyzed gem‐bis(trifluoromethyl)olefination of α‐diazo esters, using TMSCF3 as the only fluorocarbon source, has been developed and provides an exquisite method to access gem‐bis(trifluoromethyl)alkenes. This unprecedented olefination process involves a carbene migratory insertion into "CuCF3" to generate the α‐CF3‐substituted organocopper species, which then undergoes β‐fluoride elimination and two consecutive addition‐elimination processes to give the desired products. The key to this efficient one‐pot C1‐to‐C3 synthetic protocol lies in the controllable double (over single and triple) trifluoromethylations of the gem‐difluoroalkene intermediates. [ABSTRACT FROM AUTHOR]

Heteroaryl sulfones are capable of converting the carbonyl functionalities to alkenyl motifs, which is well-known as Julia–Kocienski olefination reaction. However, their sulfoxide analogues have failed in such an olefination reaction for over twenty years. In this Letter, we demonstrate that the heteroaryl sulfoxide-participated carbonyl olefination reaction can be realized under certain conditions. Furthermore, a novel defluorinative olefination of diaryl ketones has been achieved with 2-pyridyl sulfoxides. [ABSTRACT FROM AUTHOR]

Abstract: A palladium-catalyzed allylation reaction of PhSO2CH2CF3 (2) with a variety of allyl carbonates has been successfully developed for selective 2,2,2-trifluoroethylation under neutral conditions. With this method, the 1-phenylsulfonyl-2,2,2-trifluoroethyl moiety was efficiently transferred into organic compounds without the competing β-elimination of fluoride, to afford a range of mono-allylated and di-allylated compounds. [Copyright &y& Elsevier]