An efficient α-hydroxylation of carbonyls using the HOF•CH3CN complex

Dayan, Sharon; Bareket, Yífat; Rozen, Shlomo

doi:10.1016/s0040-4020(98)01173-9

Cited by 29 publications

(16 citation statements)

References 28 publications

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“…5,5′‐Dimethyl‐[2,2′]bithiophene ( 1 a )17 was cooled to −10 °C and treated with a slight excess of the acetonitrile complex of hypofluorous acid 18. The corresponding, previously unknown, bis( S , S ‐dioxide) 2 a was obtained in about 10 s and in 85 % yield.…”

Section: Methodsmentioning

confidence: 99%

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Synthesis of [all]‐S,S‐Dioxide Oligothiophenes Using HOF⋅CH₃CN

Amir

Rozen

2005

Angew Chem Int Ed

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Nonaromatic stable polyenes are obtained by dioxygenation of oligothiophenes using HOF⋅CH3CN prepared in situ by passing F2 through aqueous acetonitrile (see scheme). These fully S,S‐dioxygenated derivatives have a considerably smaller HOMO–LUMO gap than the parent compounds; furthermore, in the solid state they tend to form favorable π–π stacking interactions, unlike most non‐oxidized oligothiophenes which adopt the “herringbone” motif.

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Section: Methodsmentioning

confidence: 99%

“…A detailed procedure of how to work with F 2 and prepare HOF⋅CH 3 CN can be found in reference 18. We present a typical experiment for making the hexaoxide of the terthiophene 4 b .…”

Section: Methodsmentioning

confidence: 99%

Synthesis of [all]‐S,S‐Dioxide Oligothiophenes Using HOF⋅CH₃CN

Amir

Rozen

2005

Angew Chem Int Ed

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“…[83] Methyl mandelate (126) was obtained within 5 min from the trimethylsilyl ketene acetal of methyl phenylacetate (127) It is also possible to use acids as substrates, although the yields are somewhat lower. Reacting such ketene acetals with HOF·CH 3 CN gave indeed the α-hydroxy esters in excellent yields.…”

Section: Hydroxylations α To Carboxylic Esters and Acidsmentioning

confidence: 99%

“…Reacting such ketene acetals with HOF·CH 3 CN gave indeed the α-hydroxy esters in excellent yields. [83] Methyl mandelate (126) was obtained within 5 min from the trimethylsilyl ketene acetal of methyl phenylacetate (127) It is also possible to use acids as substrates, although the yields are somewhat lower. It is necessary to prepare the carboxylic corresponding ketene bis(trimethylsilyl acetals) which are quite sensitive to hydrolysis by the acidic aqueous media in which the HOF·CH 3 CN is present.…”

Section: Hydroxylations α To Carboxylic Esters and Acidsmentioning

confidence: 99%

Elemental Fluorine and HOF·CH₃CN in Service of General Organic Chemistry

Rozen

2005

Eur J Org Chem

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At present, HOF·CH3CN complex is the best oxygen transfer agent that chemistry has to offer. It is readily made by passing dilute fluorine through aqueous acetonitrile and does not require any isolation or purification. It is stable in aqueous acetonitrile solution for a few hours at room temperature, providing ample opportunities for various reactions. Epoxidation of regular olefins as well as of very electron‐depleted ones proceeds smoothly. HOF·CH3CN transfer oxygen also to heteroatoms, especially sulfur and nitrogen. Even very electron‐depleted sulfides such as RfSAr that are very difficult to oxidize, are converted into the respective sulfones in a matter of minutes. On the other hand, since the reaction conditions are very mild, the reagent can oxidize various thiophenes and amino acids to the corresponding S,S‐dioxides and α‐nitro acid derivatives. HOF·CH3CN was also instrumental in ending the 50 years quest for making the elusive 1,10‐phenanthroline N,N‐dioxide and for the novel transformation of azides to nitro derivatives. The use of BrF3 for making symmetric esters and of tBuOF as an electrophilic tert‐butoxylation agent is also mentioned. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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“…N-Acetylisatin, N-propionylisatin, N-benzoylisatin, N-tosylisatin under the action of NaBH 4 in THF in the presence of various nucleophiles formed biologically active derivatives of mandelic acid [35][36][37][38][39][40] (Scheme 7).…”

Section: N-acylisatinsmentioning

confidence: 99%