Trifluoromethyltrimethylsilane: Nucleophilic Trifluoromethylation and Beyond

Liu, Xiao; Xu, Cong; Wang, Mang; Li, Qun

doi:10.1021/cr400473a

Cited by 965 publications

(359 citation statements)

References 380 publications

(1,118 reference statements)

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“…Specifically, decarboxylation supposedly occurred via an outer-sphere process, which generated free − CF 3 in solution (Scheme 1C). Since free − CF 3 commonly reacts with aldehydes and ketones to generate 2,2,2,-trifluoroethanols (Scheme 2A), 10 and deprotonates acidic amides (pK a < 15 in H 2 O) 11 to generate fluoroform (pK a = 27 in H 2 O; Scheme 2B), 12 reactions that would release free − CF 3 in solution would not tolerate many important functional groups. However, we speculated that a Cu-catalyzed decarboxylation might instead occur within the solvent-sphere of the metal, and form Cu–CF 3 , which preferentially reacts with soft electrophiles.…”

Section: Cu-catalyzed Decarboxylative Trifluoromethylation Reactionsmentioning

confidence: 99%

Metal-Catalyzed Decarboxylative Fluoroalkylation Reactions

Ambler

Yang

Altman

2016

Synlett

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Metal-catalyzed decarboxylative fluoroalkylation reactions enable the conversion of simple O-based substrates into biologically relevant fluorinated analogs. Herein, we present decarboxylative methods that facilitate the synthesis of trifluoromethyl- and difluoroketone-containing products. We highlight key mechanistic aspects that are critical for efficient catalysis, and that inspired our thinking while developing the reactions.

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Section: Cu-catalyzed Decarboxylative Trifluoromethylation Reactionsmentioning

confidence: 99%

Metal-Catalyzed Decarboxylative Fluoroalkylation Reactions

Ambler

Yang

Altman

2016

Synlett

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“…2) 20–22 . An alternative approach by addition of trifluoromethyltrimethylsilane (TMSCF 3 ) to aldehydes is known; however, this method is reported to provide moderate enantioselectivity 7, 23 .…”

Section: Introductionmentioning

confidence: 99%

Synthesis of chiral α-trifluoromethyl alcohols and ethers via enantioselective Hiyama cross-couplings of bisfunctionalized electrophiles

Varenikov

Gandelman

2018

Nat Commun

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Methods for synthesis of chiral organic compounds bearing trifluoromethyl-substituted stereocenters are of great interest for agrochemical and pharmaceutical labs and industries in their search for new bioactive materials. We report on employment of bisfunctionalized electrophiles, bearing both a trifluoromethyl and a functional group as direct substituents of the reactive center, in cross-coupling reactions. We exemplify this concept in the asymmetric synthesis of enantioenriched α-trifluoromethyl- and perfluoroalkyl-containing benzylic and allylic ethers and alcohols by nickel-catalyzed stereoconvergent Hiyama cross-coupling reaction. Substrate electrophiles are conveniently prepared in few steps from trifluoroacetic acid. The method represents a conceptually different approach to chiral CF3-substituted alcohols and ethers and allows for a rapid catalytic preparation of a wide range of these valuable compounds in high yields and enantioselectivity.

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“…4 Recently, a series of fluorine reagents, such as Umemoto's reagents, [5][6][7][8][9][10] NaSO2CF3, [11][12][13][14][15] CF3SiMe3, 16 Togni's reagents, [17][18][19] and TMSCF2H, 20,21 were employed in the transformations of these fluorine functional groups. However, reports on the application of fluoroform (a cheap, nontoxic and not an ozone-depleting gas 22 ) in trifluoromethylation and difluoromethylation reactions are rare.…”

Section: Introductionmentioning

confidence: 99%

Application of fluoroform in trifluoromethylation and diﬂuoromethylation reactions

Zhang¹

2017

Arkivoc

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Recent development in the trifluoromethylation and difluoromethylation of organic compounds employing fluoroform is reviewed. Eight approaches to trifluoromethylation and difluoromethylation are summarized: (i) trifluoromethylation or difluoromethylation of carbonyl compounds, (ii) trifluoromethylation of sulfonyl fluorides, (iii) trifluoromethylation of epoxides, (iv) nucleophilic trifluoromethylation of silicon, boron, and sulfur-based compounds, (v) CuCF3 derived from fluoroform for the trifluoromethylation of aryl or heteroaryl halides, aryl boronic acids, arenediazonium salts and alkynes, (vi) difluoromethylation of alkynes, (vii) difluoromethylation of phenols, thiophenols and heterocyclic compounds, and (viii) difluoromethylation of nitriles.

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Trifluoromethyltrimethylsilane: Nucleophilic Trifluoromethylation and Beyond

Cited by 965 publications

References 380 publications

Metal-Catalyzed Decarboxylative Fluoroalkylation Reactions

Metal-Catalyzed Decarboxylative Fluoroalkylation Reactions

Synthesis of chiral α-trifluoromethyl alcohols and ethers via enantioselective Hiyama cross-couplings of bisfunctionalized electrophiles

Application of fluoroform in trifluoromethylation and diﬂuoromethylation reactions

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