Oxidation of 3-Hydroxypiperidines with Iodosylbenzene in Water: Tandem Oxidative Grob Fragmentation-Cyclization Reaction

Tada, Norio; Miyamoto, Kazunori; Ochiai, Masahito

doi:10.1248/cpb.52.1143

Cited by 10 publications

(4 citation statements)

References 12 publications

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“…Reactions with iodosylbenzene require initial depolymerization by adding a hydroxylic solvent or an appropriate catalyst (Lewis acid, bromide or iodide anion, transition metal complex, etc.). Examples of oxidation reactions with iodosylbenzene reported in our previous reviews − include the following: oxidation of alcohols, , oxidation of sulfides, , Baylis–Hillman reaction with the combination of (PhIO) n /KBr/H 2 O, radical fragmentation reaction of alcohols or amines with the PhIO·I 2 system, − oxidative Grob rearrangement of 3-hydroxyl piperidine with iodosylbenzene in water, preparation of imidazoles, thiazoles, and imidazo[1,2- a ]pyridines via α-tosyloxy carbonyl compounds using iodosylbenzene and p- toluenesulfonic acid, etc . Iodosylbenzene has also been used as a reagent for nucleophilic epoxidation of electrophilic alkenes. , …”

Section: Synthetic Applications Of Trivalent Iodine Compoundsmentioning

confidence: 99%

Advances in Synthetic Applications of Hypervalent Iodine Compounds

2016

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The preparation, structure, and chemistry of hypervalent iodine compounds are reviewed with emphasis on their synthetic application. Compounds of iodine possess reactivity similar to that of transition metals, but have the advantage of environmental sustainability and efficient utilization of natural resources. These compounds are widely used in organic synthesis as selective oxidants and environmentally friendly reagents. Synthetic uses of hypervalent iodine reagents in halogenation reactions, various oxidations, rearrangements, aminations, C−C bond-forming reactions, and transition metal-catalyzed reactions are summarized and discussed. Recent discovery of hypervalent catalytic systems and recyclable reagents, and the development of new enantioselective reactions using chiral hypervalent iodine compounds represent a particularly important achievement in the field of hypervalent iodine chemistry. One of the goals of this Review is to attract the attention of the scientific community as to the benefits of using hypervalent iodine compounds as an environmentally sustainable alternative to heavy metals.

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Section: Synthetic Applications Of Trivalent Iodine Compoundsmentioning

confidence: 99%

Advances in Synthetic Applications of Hypervalent Iodine Compounds

2016

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“…Several new oxidations with (PhIO) n have been recently reported. The oxidation of 3-hydroxypiperidine 21 with iodosylbenzene in water affords 2-pyrrolidinone 22 directly in good yield (Scheme ) . The mechanism of this reaction probably involves oxidative Grob fragmentation yielding imino aldehyde, which upon hydrolysis affords 2-pyrrolidinone by a cyclization−oxidation sequence.…”

Section: Iodine(iii) Compoundsmentioning

confidence: 99%

Chemistry of Polyvalent Iodine

2008

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“…Die Oxidation von 3‐Hydroxypiperidin ( 206 ) mit Iodosylbenzol in Wasser liefert 2‐Pyrrolidinon ( 210 , Schema ) 122. Ochiai und Mitarbeiter schlagen einen anfänglichen Ligandenaustausch von Iod(III) des Iodosylbenzols vor, wodurch das labile Aminoiodan und/oder das cyclische Iodan erzeugt wird.…”

Section: Fortschritt Und Anwendungenunclassified

C‐C‐Fragmentierung: Herkunft und jüngste Anwendungen

2013

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Sechzig Jahre sind vergangen, seit Eschenmoser und Frey den Archetyp der C‐C‐Fragmentierung beschrieben. Rasch folgten neue Fragmentierungen und mehrere Varianten des Originals. Viele dieser Variationen, einschließlich der Beckmann‐, Grob‐, Wharton‐, Marshall‐ und der Eschenmoser‐Tanabe‐Fragmentierungen, sowie weiteren, wurden im Laufe der Jahre in Übersichten besprochen, eine genaue Untersuchung des Ursprungs von Fragmentierungen steht aber noch aus. Vor kurzem tauchten neue nützliche Methoden auf, insbesondere Fragmentierungen, die zu Alkinen und Allenen führen, und solche Reaktionen wurden auf eine Reihe an komplexen Leitmotiven und Naturstoffe angewendet. Dieser Aufsatz verfolgt die Entwicklung der Fragmentierungen und bietet eine Zusammenfassung der Methoden, Anwendungen und neue Einblicke in heterolytische C‐C‐Fragmentierungen der letzten zwanzig Jahre.

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Oxidation of 3-Hydroxypiperidines with Iodosylbenzene in Water: Tandem Oxidative Grob Fragmentation-Cyclization Reaction

Abstract: Oxidation of 3-hydroxypiperidine with iodosylbenzene in water afforded 2-pyrrolidinone directly in good yields. The reaction probably involves oxidative Grob fragmentation yielding imino aldehyde, which upon hydrolysis produces 2-pyrrolidinone via a cyclization-oxidation sequence.

Cited by 10 publications

References 12 publications

Advances in Synthetic Applications of Hypervalent Iodine Compounds

Advances in Synthetic Applications of Hypervalent Iodine Compounds

Chemistry of Polyvalent Iodine

C‐C‐Fragmentierung: Herkunft und jüngste Anwendungen

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