Alkoxyl radicals from alcohols. Spectroscopic detection of intermediate alkyl and acyl hypoiodites in the Suárez and Beebe reactions

Courtneidge, John L.; Lusztyk, J.; Pagé, Daniel

doi:10.1016/s0040-4039(00)79950-3

Cited by 112 publications

(96 citation statements)

References 22 publications

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“…Compared to the standard procedure for the preparation of acetoxyhypohalites that requires the use of expensive and potentially toxic silver salts [23], our method offers a more practical alternative. It also differs from the more user-friendly protocols that rely on Oxone ® [20], DIB [24], or PIFA [25] since the iodide source is an iodide salt and not molecular iodine.…”

Section: Resultsmentioning

confidence: 99%

Iodine(III)-mediated halogenations of acyclic monoterpenoids

Peilleron¹,

Grayfer²,

Dubois³

et al. 2018

Beilstein J. Org. Chem.

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Five different halofunctionalizations of acyclic monoterpenoids were performed using a combination of a hypervalent iodine(III) reagent and a halide salt. In this manner, the dibromination, the bromo(trifluoro)acetoxylation, the bromohydroxylation, the iodo(trifluoro)acetoxylation or the ene-type chlorination of the distal trisubstituted double bond occurred with excellent selectivity and moderate to good yields.

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Section: Resultsmentioning

confidence: 99%

Iodine(III)-mediated halogenations of acyclic monoterpenoids

Peilleron¹,

Grayfer²,

Dubois³

et al. 2018

Beilstein J. Org. Chem.

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“…Based on these results, 1-methyl-, 1-ethyl-, 1-butyl-, 1,1-dimethyl-, 1-dodecyl, and 1-tridecyl-3-phenyl-1-propanols were treated with DIH in ethyl acetate and DCE to provide the corresponding chroman derivatives in good to moderate yields as shown in Table 2 (entries [1][2][3][4][5][6][7][8][9][10][11]. Under the same conditions, 3-(4¢-methylphenyl)-1-propanol and 3-(4¢-chlorophenyl)-1-propanol provided the corresponding chroman derivatives in good to moderate yields (en-…”

Section: Figurementioning

confidence: 99%

An Efficient Preparation of Chroman Derivatives from 3-Aryl-1-propanols and Related Compounds with 1,3-Diiodo-5,5-dimethylhydantoin under Irradiation Conditions

Furuyama¹,

Togo²

2010

Synlett

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P r e p a r a t i o n o f C h r o m a n D e r i v a t i v e sAbstract: Treatment of various 3-aryl-1-propanols with 1,3-diiodo-5,5-dimethylhydantoin (DIH) in ethyl acetate or 1,2-dichloroethane under irradiation with a tungsten lamp gave the corresponding chroman derivatives in good to moderate yields.The present reaction proceeds via the initial formation of an alkoxyl radical and the radical cyclization onto the aromatic ring, followed by the oxidation of the formed radical intermediate with DIH to provide the chroman derivative. The same treatment of o-biphenyldimethylcarbinol, o-phenylbenzoic acid, and o-alkylbenzoic acids with DIH provided the corresponding chroman derivatives and lactone derivatives in good yields, respectively.The use of trivalent iodines for organic synthesis has been studied widely. 1 Among them, (diacetoxyiodo)benzene (DIB) is the most popular and useful trivalent iodine reagent for organic synthesis and is used as an alternative to toxic heavy-metal reagents. 2 The advantages of DIB are that it is a nonmetal oxidant and can be used not only for polar reactions, but also for radical reactions to generate oxygen-centered radicals, nitrogen-centered radicals, and carbon-centered radicals. 3 In radical reactions, the initial formation of an unstable acetyl hypoiodite (MeCO 2 I) from the reaction with DIB and molecular iodine is the key step, and acetyl hypoiodite reacts with alcohols to form alkyl hypoiodites that would serve as the precursors of alkoxyl radicals. 4,5 Synthetic studies of alkoxyl radicals derived from substrates, such as steroidal alcohols and sugars, with DIB and molecular iodine have been well carried out by Suarez et al. 3 We have also studied the synthetic use of oxygen-centered radicals for the construction of chromans from 3-aryl-1-propanols 6 and nitrogen-centered radicals for the construction of tetrahydroquinolines, benzosultams, and saccharins from sulfonamides 7 with DIB and molecular iodine under irradiation with a tungsten lamp. On the other hand, 1,3-diiodo-5,5-dimethylhydantoin (DIH, Figure 1) is not a hypervalent iodine compound, but it may work as a synthon of unstable acetyl hypoiodite derived from the reaction with DIB and molecular iodine. Thus, this suggests that the above reactions can be carried out with DIH alone, instead of a DIB and molecular iodine system. As far as we know, the synthetic studies of DIH are extremely limited. There is one study where DIH was used for the iodination of aromatic compounds. 8 The chroman skeleton is a very important unit and is contained in some natural products, such as vitamin E and flavonoid compounds. Therefore, its synthetic study is very attractive. An extensive study of the preparation of the chroman skeleton has been carried out. 9 Figure 1Here, as part of our explorative work on the synthetic use of DIH, 10 we would like to report an efficient preparation of the chroman skeleton from 3-aryl-1-propanols and related reactions with DIH under irradiation with a tungsten lamp. Table 1 shows the results of the r...

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“…12 O-I bond cleavage in RCO 2 I under heating or irradiation conditions occurs smoothly to give an acyloxy radical (RCO 2 ·) and an iodine atom. Once the acyloxy radical is formed, it rapidly decomposes to a carbon-centered radical (R·) and CO 2 via the b-cleavage (Eq.…”

Section: Carbon-centered Radicalsmentioning

confidence: 99%

Synthetic Uses of Organohypervalent Iodine Compounds Through Radical Pathways

Togo¹,

Katohgi²

2001

Synlett

167

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Hypervalent iodine compounds, especially (diacetoxyiodo)arenes, have been used for the generation of (a) carbon-centered radicals through the decarboxylation of carboxylic acids or the β-cleavage of alcohols, (b) oxygen-centered radicals from alcohols, hemi-acetals, or carboxylic acids, (c) nitrogen-centered radicals from amine derivatives. The radicals were employed for β-fragmentation, oxidative addition and substitution, Barton-type reactions, Hofmann-Löffler-Freytag-type reactions, and reductive addition reactions, and successfully used for functional group transformation, formation of new skeletons and synthesis of natural products.

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Alkoxyl radicals from alcohols. Spectroscopic detection of intermediate alkyl and acyl hypoiodites in the Suárez and Beebe reactions

Cited by 112 publications

References 22 publications

Iodine(III)-mediated halogenations of acyclic monoterpenoids

Iodine(III)-mediated halogenations of acyclic monoterpenoids

An Efficient Preparation of Chroman Derivatives from 3-Aryl-1-propanols and Related Compounds with 1,3-Diiodo-5,5-dimethylhydantoin under Irradiation Conditions

Synthetic Uses of Organohypervalent Iodine Compounds Through Radical Pathways

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