Stable fluorinated sulfuranes and sulfurane oxides. Synthesis and reactions

Kitazume, Tomoya; Shreeve, Jean’ne M.

doi:10.1021/ic50186a029

Cited by 33 publications

(11 citation statements)

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“…[30] A mechanism based on nucleophilic attack of the phenol on the sulfurane followed by intramolecular rearrangement was proposed. [30] A mechanism based on nucleophilic attack of the phenol on the sulfurane followed by intramolecular rearrangement was proposed.…”

Section: Oxidative Couplings Between Alcohols and Nucleophilic Triflumentioning

confidence: 99%

“…The synthesis of (trifluoromethoxy)benzene and paratrifluoromethoxytoluene was achieved using sulfurane or sulfurane oxide (Scheme 7). [30] A mechanism based on nucleophilic attack of the phenol on the sulfurane followed by intramolecular rearrangement was proposed. However, this method could not be employed for the trifluoromethylation of secondary or tertiary alkyl alcohols as only the corresponding alkenes were formed.…”

Section: Phenol Trifluoromethylation Through Phenol Activation and Ip...mentioning

confidence: 99%

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Synthetic Approaches to Trifluoromethoxy‐Substituted Compounds

2016

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Because of the unique properties of the trifluoromethoxy group, molecules bearing this moiety will find applications in various fields, particularly in the life sciences. However, despite the great interest in this functional group, only a small number of trifluoromethoxylated molecules are currently synthetically accessible. Over the last few years, several innovative and promising strategies for the synthesis of trifluoromethoxylated compounds have been described. This Minireview discusses these existing methods with a particular focus on more recent advances.

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Section: Oxidative Couplings Between Alcohols and Nucleophilic Triflumentioning

confidence: 99%

Section: Phenol Trifluoromethylation Through Phenol Activation and Ip...mentioning

confidence: 99%

Synthetic Approaches to Trifluoromethoxy‐Substituted Compounds

2016

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“…Ein ahnliches Verhalten findet man auch bei dem Sulfoxylat S[OCH(CF,),], 1 [4], welches mit Chlor zwar nicht das erwartete Sulfuran [5] C1,S[OCH(CF3),l2 ergibt,, wohl aber dessen Dismutierungsprodukt ClS[OCH(CF,),], 2 [4]. Sulfoxylsaureester S(OR), (R = Alk) [6] setzen sich rnit Chlor zu Produkten um, die den Ablauf einer Arbuzov-Umlagerung ahnlichen Reaktion wahrscheinlich machen Das Sulfuran 2 zersetzt sich nicht zu dem Schwefligsaureester ClS( : 0)OCH-(CF,), [7] und ClCH(CF,),, wohl aber beim Erwarmen, in iihnlicher Weise wie verwandte Alkoxysulfurane [8] 21 3 Mit Trimethylphosphin setzt sich 2 nicht zu einem Derivat des pentakoordinierten Phosphors urn (GI. Vakuum abgezogen und fraktionierend kondensiert.…”

Section: Reactions Of Cls[och(cfand]3 and S[och(cf3)2]2 With Phosphorusunclassified

Reaktionen von ClS[OCH(CF₃)₂]₃ und S[OCH(CF₃)₂]₂ mit Phosphor(III)‐Verbindungen

Röschenthaler

1981

Zeitschrift anorg allge chemie

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Das Sulfuran ClS[OCH(CF3)2]3 reagiert mit Me3P zu dem Phosphoniumsalz [Me3POCH(CF3)2]+Cl−, mit (MeO)3P im Sinne einer Arbuzov‐Reaktion zu (MeO)2P(:O)OCH(CF3)2 und MeCl. Bei beiden Umsetzungen wird das Sulfuran zu dem Sulfoxylat S[OCH(CF3)2]2 reduziert. Derivate des pentakoordinierten Phosphors werden mit dem cyclischen Phosphit FP[OC(CF3)2O] und P[OCH(CF3)2]3 erhalten. Das Sulfoxylat S[OCH(CF3)2]2 ist ebenfalls in der Lage Me3P, (MeO)3P und P[OCH(CF3)2]3 zu R3PO und R3PS (R = OMe, OCH(CF3)2) zu oxidieren. Weiteres Produkt dieser Umsetzung ist der Ether (CF3)2CHOCH(CF3)2.

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“…In theory,d irect trifluoromethoxylation is the ideal method for the preparation of trifluoromethyl ether-containing compounds but despite the tremendous effort devoted to the development of nucleophilic trifluoromethoxylation reagents, the reported nucleophilic trifluoromethoxylating reagents have shortcomings.A mong earlier reports,s ulfurane and its oxide,( CF 3 ) 2 S(O) n (OCF 3 ) 2 (n = 0, 1), converted phenols to (trifluoromethoxy)benzenes via nucleophilic attack of the CF 3 Om oiety. [8] However,t he preparation of sulfuranes required as pecial technique that used very toxic and explosive compounds. [9] More recently,t rifluoromethyl triflate (TFMT) [10] was employed as anucleophilic reagent with fluoride to prepare alkyl and aryl trifluoromethyl ethers.…”

Section: Introductionmentioning

confidence: 99%

Trifluoromethyl Nonaflate: A Practical Trifluoromethoxylating Reagent and its Application to the Regio‐ and Stereoselective Synthesis of Trifluoromethoxylated Alkenes

Kumon

Hammond

et al. 2021

Angew Chem Int Ed

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The trifluoromethoxy group has elicited much interest among drug and agrochemical discovery teams because of its unique properties. We developed trifluoromethyl nonafluorobutanesulfonate (nonaflate), TFNf, an easy‐to‐handle, bench‐stable, reactive, and scalable trifluoromethoxylating reagent. TFNf is easily and safely prepared in a simple process in large scale and the nonaflyl part of TFNf can easily be recovered as nonaflyl fluoride after usage and recycled. The synthetic potency of TFNf was showcased with the underexplored synthesis of various trifluoromethoxylated alkenes, through a high regio‐ and stereoselective hydro(halo)trifluoromethoxylation of alkyne derivatives such as haloalkynes, alkynyl esters, and alkynyl sulfones. The synthetic merits of TFNf were further underscored with a high‐yielding and smooth nucleophilic trifluoromethoxylation of alkyl triflates/bromides and primary/secondary alcohols.

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Stable fluorinated sulfuranes and sulfurane oxides. Synthesis and reactions

Cited by 33 publications

References 3 publications

Synthetic Approaches to Trifluoromethoxy‐Substituted Compounds

Synthetic Approaches to Trifluoromethoxy‐Substituted Compounds

Reaktionen von ClS[OCH(CF₃)₂]₃ und S[OCH(CF₃)₂]₂ mit Phosphor(III)‐Verbindungen

Trifluoromethyl Nonaflate: A Practical Trifluoromethoxylating Reagent and its Application to the Regio‐ and Stereoselective Synthesis of Trifluoromethoxylated Alkenes

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Stable fluorinated sulfuranes and sulfurane oxides. Synthesis and reactions

Cited by 33 publications

References 3 publications

Synthetic Approaches to Trifluoromethoxy‐Substituted Compounds

Synthetic Approaches to Trifluoromethoxy‐Substituted Compounds

Reaktionen von ClS[OCH(CF3)2]3 und S[OCH(CF3)2]2 mit Phosphor(III)‐Verbindungen

Trifluoromethyl Nonaflate: A Practical Trifluoromethoxylating Reagent and its Application to the Regio‐ and Stereoselective Synthesis of Trifluoromethoxylated Alkenes

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Reaktionen von ClS[OCH(CF₃)₂]₃ und S[OCH(CF₃)₂]₂ mit Phosphor(III)‐Verbindungen