Base‐Catalyzed Electrophilic Trifluoromethylthiolation of Terminal Alkynes

Alazet, Sébastien; Zimmer, Luc; Billard, Thierry

doi:10.1002/ange.201305179

Cited by 48 publications

(10 citation statements)

References 82 publications

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“…Furthermore, the similarity of the thioperoxide structure to the previously reported nitrogen-based electrophilic trifluoromethylthiolation reagents by the groups of Billard [16] and Rueping [17] (Scheme 4a and b), as well as the disulfide reagents used for directed Cu-promoted sulfenylation of sp 2 C–H bonds by Daugulis et al [18] (Scheme 4c) supports the hypothesis that the observed reactivity [1a,c] could arise from the thioperoxide fragment itself.…”

supporting

confidence: 74%

Structural Reevaluation of the Electrophilic Hypervalent Iodine Reagent for Trifluoromethylthiolation Supported by the Crystalline Sponge Method for X‐ray Analysis

2014

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Hypervalent iodine λ3-benziodoxoles are common electrophilic transfer reagents known for their enhanced stability compared to their non-cyclic analogues. Herein we present data showing that chlorobenziodoxole reacts with two different thiolate nucleophiles (thiocyanate and trifluoromethylthiolate), resulting in the formation of stable thioperoxy complexes rather than the expected benziodoxole derivatives. We further report a revised structure for the earlier described electrophilic trifluoromethylthiolation reagent (1), which was previously believed to contain the benziodoxole framework. Our findings, which are based on a combination of analytical techniques, including the recently introduced crystalline sponge method for X-ray analysis, unambiguously demonstrate that 1 is a thioperoxy compound both in solution and the solid state.

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supporting

confidence: 74%

Structural Reevaluation of the Electrophilic Hypervalent Iodine Reagent for Trifluoromethylthiolation Supported by the Crystalline Sponge Method for X‐ray Analysis

2014

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“…Longer reaction times do not increase the yield, the reaction seems to be finished in 15 min (Table 1, entries 2 and 3). As previously observed in other works, the use of other bases with sodium or cesium cations is not efficient since only Li is a Lewis acid strong enough to activate 1a [38,44]. These optimal conditions have been extended to selected amines 2 (Fig.…”

Section: Resultsmentioning

confidence: 84%

Direct electrophilic N-trifluoromethylthiolation of amines with trifluoromethanesulfenamide

Alazet¹,

Ollivier²,

Billard³

2013

Beilstein J. Org. Chem.

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“…that trifluoromethylation of both vinyl trifluoroborates and alkynyl trifluoroborates can be accomplished by employing electrophilic trifluoromethylating reagents 1 a and 1 b, respectively, albeit under very different reaction conditions. [31,[42][43][44] Terminal aryl acetylene derivatives have also been reported by Weng, Huang and co-workers to be trifluoromethylated with reagent 1 b in the presence of 1,10-phenanthroline as ligand, CuI as catalyst, KHCO 3 as base, in CH 2 Cl 2 as solvent in yields ranging from 70-98 %, [45] according to Scheme 25.…”

Section: Formation Of C(sp 2 )àCf 3 Bondsmentioning

confidence: 81%

Recent Advances in Trifluoromethylation Reactions with Electrophilic Trifluoromethylating Reagents

Barata‐Vallejo

Lantaño

Postigo

2014

Chemistry A European J

342

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Electrophilic trifluoromethylation reactions have been the latest approach to achieve the fluoroalkylation of compounds with newly-discovered reagents, such as the Togni's (1-trifluoromethyl-1,2-benziodoxol-3-(1 H)-one), Umemoto's (S-(trifluoromethyl)dibenzothiophenium tetrafluoroborate), Yagupolskii's (S-(trifluoromethyldiarylsulfonium salts), Shreeve's (S-(trifluoromethyl)dibenzothiophenium triflate), and Shibata's (trifluoromethylsulfoximine salts) reagents. All these reagents produce an electrophilic trifluoromethylating (CF3 (+) ) species that undergoes reaction with nucleophiles. In addition, these latter reactive species (i.e. CF3 (+) ) can undergo electron-transfer (ET) processes affording CF3 (⋅) radicals that expand the scope to substrates other than conventional nucleophiles that can undergo reaction. In this Review, we shall discuss the trifluoromethylation reactions of diverse families of organic substrates of biological interest as a means to comparing the reagents scope and best reaction conditions. Some, though not all, of these reactions require the assistance of metal or organometallic catalysts. Some require additives and catalysts to promote the fluoroalkylation reaction, but invariably all are initiated and carried out by electrophilic trifluoromethylating species.

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Base‐Catalyzed Electrophilic Trifluoromethylthiolation of Terminal Alkynes

Cited by 48 publications

References 82 publications

Structural Reevaluation of the Electrophilic Hypervalent Iodine Reagent for Trifluoromethylthiolation Supported by the Crystalline Sponge Method for X‐ray Analysis

Structural Reevaluation of the Electrophilic Hypervalent Iodine Reagent for Trifluoromethylthiolation Supported by the Crystalline Sponge Method for X‐ray Analysis

Direct electrophilic N-trifluoromethylthiolation of amines with trifluoromethanesulfenamide

Recent Advances in Trifluoromethylation Reactions with Electrophilic Trifluoromethylating Reagents

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