The Synthesis and Oxidative Properties of Polymer-Supported IBX

Mülbaier, Marcel; Giannis, Athanassios

doi:10.1002/1521-3773(20011203)40:23<4393::aid-anie4393>3.0.co;2-2

Cited by 133 publications

(46 citation statements)

References 11 publications

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“…Based on the remarkable acceleration of the oxidation of phenols by addition of only a small amount of iodoarene and documented examples of the reactions of iodoarene and Oxone ® , which produce pentavalent iodine species, [43][44][45][46][47][48] it was suggested that iodine(V) species, generated in situ, was included in this oxidation as the active catalyst. However, formation of pentavalent iodine species requires a higher temperature (70°C) than that in the oxidation of 2 with 1a and Oxone ® .…”

Section: Resultsmentioning

confidence: 99%

Catalytic Hypervalent Iodine Oxidation Using 4-Iodophenoxyacetic Acid and Oxone: Oxidation of p-Alkoxyphenols to p-Benzoquinones

Yakura

Tian

Yamauchi

et al. 2009

CHEMICAL & PHARMACEUTICAL BULLETIN

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Hypervalent iodine compounds, trivalent iodine compounds such as phenyliodine(III) diacetate (PIDA) and phenyliodine(III) trifluoroacetate (PIFA) and pentavalent iodine reagents such as Dess-Martin periodinane (DMP) and o-iodoxybenzoic acid (IBX), have been used extensively in recent organic synthesis because of their low toxicity, ready availability and easy handling. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] However, these reagents are highly expensive. And stoichiometric amounts of iodine reagents are required to produce equimolar amounts of organic iodine waste. Moreover, pentavalent iodine reagents are potentially explosive. To overcome these disadvantages, catalytic hypervalent iodine oxidations [16][17][18] using mchloroperbenzoic acid (m-CPBA), [19][20][21][22][23][24][25][26][27] Oxone ® (2KHSO 5 · KHSO 4 · K 2 SO 4 ), 28,29) and H 2 O 2 30) as a co-oxidant have been reported recently.Development of efficient methods for synthesis of pquinone and p-quinone derivatives is an important subject in synthetic organic chemistry because they are structural components of numerous natural products and useful synthetic intermediates. [31][32][33][34][35][36] A convenient procedure for p-quinones was hypervalent iodine oxidation of p-alkoxyphenols using PIFA.37) Reactions of p-alkoxyphenols with an equimolar amount of PIFA in a 2 : 1 mixture of acetonitrile and water at room temperature gave the corresponding p-quinones in excellent yield.As part of our study for development of practical and environmentally benign oxidation, we report a mild, efficient and practical procedure for catalytic hypervalent iodine oxidation of p-alkoxyphenols to p-quinones using a catalytic amount of 4-iodophenoxyacetic acid (1a) and Oxone ® as a co-oxidant 38) in 2,2,2-trifluoroethanol-water. Results and DiscussionWe chose Oxone ® as an environmentally safe co-oxidant for a catalytic hypervalent iodine oxidation of p-alkoxyphenols because Oxone ® is an inorganic and water-soluble oxidant with a low order of toxicity, moreover, it is commercially available and inexpensive. 39) Oxone ® has been already used as a co-oxidant under heating conditions in the catalytic IBX oxidation by Vinod 28) and Giannis 29) groups, independently. Because alkoxyphenols have high reactivity under oxidation conditions, we first investigated the oxidative ability of Oxone ® itself. 40) A mixture of 2-pivaloyloxymethyl-4-methoxyphenol (2a) and an equimolar amount of Oxone ® in acetonitrile-water (2 : 1) at room temperature gave the corresponding p-benzoquinone (3a), but the reaction was sluggish and the yield of 3a was only 13% along with 78% of recovered starting 2a after 24 h. Next, we examined reactions of 2a in the presence of several iodoarenes as a catalyst (Chart 1). Table 1 presents the results. According to the procedure reported by Vinod, 28) a mixture of 2a, 0.2 equivalents (eq) of 2-iodobenzoic acid, and 1 eq of Oxone ® in acetonitrile-water was heated at 70°C for 19 h to give a complicated mixture (entry 2). However, a similar reactio...

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Section: Resultsmentioning

confidence: 99%

Catalytic Hypervalent Iodine Oxidation Using 4-Iodophenoxyacetic Acid and Oxone: Oxidation of p-Alkoxyphenols to p-Benzoquinones

Yakura

Tian

Yamauchi

et al. 2009

CHEMICAL & PHARMACEUTICAL BULLETIN

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“…It is interesting to mention that these observations together with the recent report on polymer-supported IBX 15 could be useful to develop green sequences toward biologically active steroids.…”

Section: Resultsmentioning

confidence: 87%

An efficient and environmentally benign chemical synthesis of testolactone

Zinczuk

Bacigaluppo

Colombo

et al. 2003

J. Braz. Chem. Soc.

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Um estudo comparativo é descrito para dois ensaios da síntese do esteróide testolactona de interesse biológico. O primeiro ensaio é clássico e eficiente. No segundo ensaio reagentes de risco foram substituídos por alternativos não perigosos, mantendo-se o mesmo grau de eficiência.A comparative study of two approaches for the chemical synthesis of the biologically interesting steroid testolactone is described. The first approach is efficient but classical, in the second one, hazardous chemicals were replaced by benign alternatives maintaining the same degree of efficiency.

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“…Prior studies have emphasized the use of a variety of insoluble supports for this purpose. 14 These previous studies have reported the use of both inorganic supports like silica gel 15 and organic polymer supports like crosslinked polystyrene. 16,17 These studies that immobilized IBX oxidants were precedented by earlier work by the Moss group who also immobilized iodosobenzoate reagents on polystyrene.…”

Section: Contents Lists Available At Sciencedirectmentioning

confidence: 99%

Recyclable soluble polyisobutylene-bound oxidizing agents

Samunual

Bergbreiter

2016

Tetrahedron Letters

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a b s t r a c tThis Letter describes the use of alkene-terminated polyisobutylene (PIB) as a support for oxidizing agents. Two oxidizing agents, an ionically immobilized PIB-bound perruthenate oxidation catalyst and a PIBbound 2-iodoxybenzoic acid (IBX) oxidizing reagent, were studied. A perruthenate catalyst ionically bound to PIB was prepared by binding the perruthenate anion to PIB that contained either a terminal tetraalkylammonium or an imidazolium salt. The PIB supported ammonium and imidazolium perruthenate were both selectively soluble in heptane and effective in the oxidation of alcohols. While these PIBbound perruthenate catalysts could be readily separated from products, recycling was less successful. A PIB bound 2-iodoxybenzoic (IBX) oxidizing agent was coupled to a PIB support with an ester bond. It was highly soluble in nonpolar and moderately polar organic solvents. By taking advantage of PIB's heptane solubility, the spent IBX reagent could be easily separated from products by a liquid/liquid heptane/acetonitrile biphasic separation. The recovered IBX reagent could then be regenerated and used in multiple cycles for oxidation of both primary and secondary alcohols.

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The Synthesis and Oxidative Properties of Polymer-Supported IBX

Abstract: Primary and secondary alcohols are oxidized smoothly under mild conditions and in high yields to the corresponding aldehydes and ketones by 1 (see scheme), the first polymer‐supported IBX.

Cited by 133 publications

References 11 publications

Catalytic Hypervalent Iodine Oxidation Using 4-Iodophenoxyacetic Acid and Oxone: Oxidation of p-Alkoxyphenols to p-Benzoquinones

Catalytic Hypervalent Iodine Oxidation Using 4-Iodophenoxyacetic Acid and Oxone: Oxidation of p-Alkoxyphenols to p-Benzoquinones

An efficient and environmentally benign chemical synthesis of testolactone

Recyclable soluble polyisobutylene-bound oxidizing agents

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