Oxidative Cleavage of Methyl Ethers Using the HOF.cntdot.CH3CN Complex

Rozen, Shlomo; Dayan, Sharon; Bareket, Yífat

doi:10.1021/jo00130a029

Cited by 35 publications

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“…We have also demonstrated that this reagent is able to perform the very rare transformation of oxidizing methyl ethers to ketones by the nonclassical 3-center-2-electrons carbonium ion mechanism placing the 18 O isotope in the resulting carbonyl (Scheme 3). [29] Scheme 3. Methyl ether oxidation.…”

Section: General Backgroundmentioning

confidence: 99%

“…[28,29] The hydroxy group, however, could be easily oxidized with chromic acid (Jones reagent) forming the desired 116, 118 and 119 in 65 % overall yield (Scheme 30). The reagent was not able, though, to further oxidize the hydroxy group since alcohol oxidation with HOF·CH 3 CN proceeds through an abstraction of the geminal hydrogen that in these cases form relatively electrondeficient C-H bonds.…”

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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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Section: General Backgroundmentioning

confidence: 99%

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

Rozen

2005

Eur J Org Chem

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“…Ketones also undergo Baeyer-Villiger oxidation to give esters under the same reaction conditions. 7 All these reactions are ionic in nature.…”

Section: Preparationmentioning

confidence: 99%

HOF·CH₃CN Complex

Gogoi¹

2005

Synlett

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This feature focuses on a reagent chosen by a postgraduate, highlighting the uses and preparation of the reagent in current research HOF•CH 3 CN Complex Compiled by Siddhartha GogoiSiddhartha Gogoi was born in Sivasagar, Assam (India) in 1977. He completed his B.Sc. (1998) degree from Dibrugarh University and M.Sc. (2000) degree in chemistry from Gauhati University, Guwahati (India). He is currently working toward a Ph.D. in organic chemistry under the supervision of Dr. N. C. Barua at the Regional Research Laboratory in Jorhat, India. His research interests are the total synthesis of bioactive natural products and the development of new methodologies.

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“…Besonders Rozen und seine Arbeitsgruppe führten 1 als potentes Sauerstofftransferreagens für viele Umwandlungen ein, darunter auch solche, die für bestimmte Substrate als problematisch galten: Sie verwendeten das Reagens zur Synthese von Epoxiden aus Olefinen, [7] von Ketonen aus Methylethern, [8] von Estern durch die Baeyer-VilligerReaktion, [9] von Sulfonen aus Sulfanen, [10] von Nitroverbindungen aus Aminen [11] und Aminosäuren, [12] von N-Oxiden aus tertiären Aminen [13] sowie für weitere Umwandlungen. [14] Darüber hinaus ist isotopenmarkiertes [15] Die Hypofluorige Säure, HOF, blickt auf eine interessante Geschichte zurück: [16] Zwar behauptete man schon 1932 zum ersten Mal, diese Verbindung hergestellt zu haben, [17] doch als offizielles Geburtsjahr von HOF gilt 1968, als Noble und Pimentel die Verbindung in einer festen Stickstoffmatrix eindeutig IR-spektroskopisch charakterisierten.…”

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