Stereoselective Synthesis of 5-7 membered Cyclic Ethers by Deiodonative Ring-Enlargement Using Hypervalent Iodine Reagents

Abo, Tomohito; Sawaguchi, Masanori; Senboku, Hisanori; Hara, Shoji

doi:10.3390/10010183

Cited by 17 publications

(7 citation statements)

References 16 publications

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“…[Bis(acyloxy)iodo]arenes-promoted rearrangements have been applied in various ring expansion or ring contraction reactions, − Hofmann rearrangement, − and Claisen rearrangement. − …”

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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“…[Bis(acyloxy)iodo]arenes-promoted rearrangements have been applied in various ring expansion or ring contraction reactions, − Hofmann rearrangement, − and Claisen rearrangement. − …”

Section: Synthetic Applications Of Trivalent Iodine Compoundsmentioning

confidence: 99%

Advances in Synthetic Applications of Hypervalent Iodine Compounds

2016

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“…In developing such a method, we took inspiration from the Criegee rearrangement of activated alkyl peroxides, wherein the O–O bond is labilized via reaction with an anhydride, promoting C-to-O migration (Scheme A). , We envisioned an analogous transformation in the context of simple alcohols via electrophilic activation with a hypervalent iodine reagent (Scheme B). − Attack of the alcohol on the iodine center would generate an activated intermediate ( 4 ) wherein the oxygen is now electrophilic. This sets the stage for a carbon-to-oxygen alkyl migration, driven by the loss of iodine in its normal valency (IAr), and the resultant oxonium ion ( 5 ) could be trapped by a nucleophile to give the functionalized ether scaffold ( 6 ).…”

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confidence: 99%

Access to Diverse Oxygen Heterocycles via Oxidative Rearrangement of Benzylic Tertiary Alcohols

2016

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A facile method for the synthesis of challenging medium-sized cyclic ethers has been developed via a novel oxidative rearrangement of benzylic tertiary alcohols. The reaction provides access to cyclic acetals with diverse substitution at both C2 and the aromatic ring. The unique reactivity is enabled by poly(cationic) hypervalent iodine reagents and represents the first synthetic application of this underexplored class of compounds.

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“…Hypervalent iodine reagents, readily available, nontoxic, and environmental benign, have been reported to act as electrophiles to activate the double bonds in alkenes, which initiate oxidative rearrangement through ring expansion, ring contraction, or aryl migration. − , Koser’s group reported the first hydroxytosyloxy iodobenzene (HTIB)-mediated oxidative rearrangement of 1,1-diphenylethylene, which later expanded to a versatile type of arylalkenes and cyclic arylalkenes . Purohit and co-workers demonstrated an efficient catalytic use of iodine compounds which generated I(III) in situ to furnish the oxidative 1,2-aryl shift of 1,1-disubstituted olefins (Scheme , a).…”

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confidence: 99%