1-[Hydroxy(sulfonyloxy)iodo]-1<i>H</i>,1<i>H</i>-perfluoroalkanes:  Stable, Fluoroalkyl Analogs of Koser's Reagent

Zhdankin, Viktor V.; Kuehl, C. J.; Simonsen, Angela J.

doi:10.1021/jo961336n

Cited by 46 publications

(31 citation statements)

References 21 publications

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Section: Mechanism Discussionmentioning

confidence: 99%

“…The formation of cis-and trans-isomers has also been observed in the reaction of indene with iodosobenzene derivatives in methanol. 30 However, the oxidation of cyclohexenes with iodine(III) led to rearrangement products, 6 cis-isomers 6,[31][32][33] or trans-isomers, 31,34 depending mainly on the reaction conditions.As described above, the solvent has a crucial role in the oxidation of 1,2-dihydronaphthalenes with HTIB. In methanol, ring contraction is favored toward the addition of solvent for disubstituted double bonds.…”

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confidence: 99%

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Metal-free synthesis of indanes by iodine(III)-mediated ring contraction of 1, 2-dihydronaphthalenes

Siqueira¹,

Ishikawa²,

Fogaça³

et al. 2011

J. Braz. Chem. Soc.

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Um protocolo livre de metais foi desenvolvido para sintetizar indanos através da contração de anel de 1,2-di-hidronaftalenos promovida por PhI(OH)OTs (HTIB ou reagente de Koser). Este rearranjo oxidativo pode ser realizado em diversos solventes (MeOH, CH 3 CN, 2,2,2-trifluoroetanol (TFE), 1,1,1,3,3,3-hexafluoroisopropanol (HFIP), e uma mistura 1:4 de TFE:CH 2 Cl 2 ) em condições brandas. A contração de anel fornece indanos trans-1,3-dissubstituídos diastereosseletivamente, os quais são difíceis de obter em química orgânica sintética.A metal-free protocol was developed to synthesize indanes by ring contraction of 1,2-dihydronaphthalenes promoted by PhI(OH)OTs (HTIB or Koser's reagent). This oxidative rearrangement can be performed in several solvents (MeOH, CH 3 CN, 2,2,2-trifluoroethanol (TFE), 1,1,1,3,3,3-hexafluoroisopropanol (HFIP), and a 1:4 mixture of TFE:CH 2 Cl 2 ) under mild conditions. The ring contraction diastereoselectively gives functionalized trans-1,3-disubstituted indanes, which are difficult to obtain in synthetic organic chemistry.Keywords: indanes, hypervalent iodine, ring contraction, 1,2-dihydronaphthalenes, rearrangements IntroductionThe indane ring system is present in several natural products and in non-natural compounds with remarkable biological activity.1 Consequently, efforts have continuously been made to develop new routes to obtain molecules with this unit.2 A typical strategy to synthesize a functionalized indane is by selecting an appropriate indanone, which is then elaborated into the target molecule. 2,3 As tetralones are usually cheaper than indanones, the preparation of indanes starting from a tetralone (or a derivative) through a ring contraction rearrangement could be advantageous. 4 In the last years, hypervalent iodine reagents have become an essential tool in synthetic organic chemistry due to the plethora of reactions that can be performed with them in excellent yield and selectivities. 5 Moreover, hypervalent iodine compounds represent in many cases an alternative to toxic heavy metals. 5 Although the oxidative rearrangement of alkenes mediated by iodine(III) has been described in some papers, 6 the ring contraction of 1,2-dihydronaphthalenes was reported for a few substrates using only p-Me-C 6 H 4 -IF 2 , 6 which led to fluorinated indanes.Herein, we describe an efficient metal-free protocol for the synthesis of indanes under mild conditions. In a preliminary communication, we report the ring contraction of 1,2-dihydronaphthalenes (which are obtained from 1-tetralones) mediated by PhI(OH)OTs (HTIB or Koser's reagent) for a few substrates. 7 In this article, the oxidation of several additional substrates is presented, better defining the reaction scope. Additionally, other reaction conditions were Metal-Free Synthesis of Indanes by Iodine(III)-Mediated Ring Contraction J. Braz. Chem. Soc. 1796 discovered using fluoroalcohols as solvent, which highly improved isolated yields. The best condition employed a 4:1 mixture of CH 2 Cl 2 -TFE that led to indanes in...

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Section: Mechanism Discussionmentioning

confidence: 99%

mentioning

confidence: 99%

Metal-free synthesis of indanes by iodine(III)-mediated ring contraction of 1, 2-dihydronaphthalenes

Siqueira¹,

Ishikawa²,

Fogaça³

et al. 2011

J. Braz. Chem. Soc.

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“…A useful approach to polyfluoroalkyl(aryl)iodonium sulfonates and polyfluoroalkyl(alkynyl)iodonium sulfonates was elaborated by Zhdankin et al [59][60][61]. They found out that 1-[hydroxy(sulfonyloxy)iodo]-1H,1H-perfluoroalkanes (see Section 3, Eq.…”

Section: Umemoto Et Al Improved This Methods Significantly By Using Tmentioning

confidence: 99%

Polyvalent perfluoroorgano- and selected polyfluoroorgano-halogen(III and V) compounds

Frohn

Hirschberg

Wenda

et al. 2008

Journal of Fluorine Chemistry

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“…For the general preparation of [hydroxy(organosulfonyloxy)iodo]arenes 298 , [hydroxy(tosyloxy)iodo]heteroarenes 299 – 301 , recyclable [hydroxy(tosyloxy)iodo]arenes 302 – 306 , and a polymer-supported [hydroxy(tosyloxy)iodo]benzene 307 (Figure ), the ligand exchange reaction with an appropriate organosulfonic acid and [bis(acyloxy)iodo]arenes is usually used. ,,− Likewise, numerous polyfluoroalkyl derivatives of the types C n F 2 n +1 I(OH)OTs 308 ,, and C n F 2 n +1 CH 2 I(OH)OTs 309 , can be prepared by treatment of the respective polyfluoroalkyliodo bis(trifluoroacetates) with p -toluenesulfonic acid.…”

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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1-[Hydroxy(sulfonyloxy)iodo]-1H,1H-perfluoroalkanes: Stable, Fluoroalkyl Analogs of Koser's Reagent

Cited by 46 publications

References 21 publications

Metal-free synthesis of indanes by iodine(III)-mediated ring contraction of 1, 2-dihydronaphthalenes

Metal-free synthesis of indanes by iodine(III)-mediated ring contraction of 1, 2-dihydronaphthalenes

Polyvalent perfluoroorgano- and selected polyfluoroorgano-halogen(III and V) compounds

Advances in Synthetic Applications of Hypervalent Iodine Compounds

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