The Rearrangement of Allyl Ethers to Propenyl Ethers

Prosser, Thomas

doi:10.1021/ja01468a035

Cited by 104 publications

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“…It should be noted that we observed no further transformations of 3-(2-propynyloxy)propan-2-ols IIa and IIb, such as prototropic rearrangements in the 2-propynyl or allyl (in IIa) fragments (e.g., acetyleneallene [12,23] and/or allyl-propenyl isomerization [24][25][26]) or intramolecular cyclizations involving hydroxy group and triple bond [2][3][4][5][6][7][8]12], which are usually promoted by bases. A probable reason is the low concentration of the catalyst (~0.05 mol per mole of oxirane).…”

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confidence: 81%

“…The most probable reason is relatively low temperature (60°C) and insufficient reaction time (3 h). As shown in [26], prototropic rearrangement of allyl ethers under solvent-free conditions requires heating to 150-175°C over a period of 3-163 h in the presence of 2-15 wt % of base catalyst (t-BuOK, MeONa) in a nitrogen atmosphere (yield 35-99%).…”

Section: Iia-viiia Iic-viiicmentioning

confidence: 99%

“…As we already noted, apart from the heterocyclizations and acetylene-allene rearrangement considered above, 1-allyloxy-3-(2-propynyloxy)propan-2-ol (IIa) 1439 and its derivatives IIIa-VIIIa can be involved in another base-catalyzed prototropic isomerization, namely allyl-propenyl rearrangement [24][25][26] which implies migration of the double C=C. Insofar as preparative version of that rearrangement was not the aim of the present study, we did not optimize its conditions but only analyzed the NMR spectra of the products obtained under the conditions summarized in Tables 2 and 3, as well as in other experiments.…”

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confidence: 95%

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Vinyl Ethers Containing an Epoxy Group: XXII. Synthesis and Base-Catalyzed Transformations of 1-(Allyloxy)- and 1-[2-(Vinyloxy)ethoxy]-3-(2-propynyloxy)propan-2-ols

et al. 2005

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Reactions of 2-(allyloxymethyl)-and 2-[2-(vinyloxy)ethoxy]methyloxiranes with 2-propynol (~3 wt % of t-BuOK, 75-85°C, 5-10 h) lead to formation of new 1-organyloxy-3-(2-propynyloxy)propan-2-ols (yield 65-95%). On heating to 45-100°C in the presence of bases (KOH, t-BuOK), 1-allyloxy-and 1-[2-(vinyloxy)ethoxy]-3-(2-propynyloxy)propan-2-ols are transformed into the corresponding 2-vinyl-1,3-dioxolane, 6-methyl-2,3-dihydro-1,4-dioxine, 6-methylene-1,4-dioxane, and 2,3-dihydro-5H-1,4-dioxepine derivatives, whose yield and ratio strongly depend on the solvent nature, catalyst, and substituent at the hydroxy group. 2-Vinyl-1,3-dioxolane and 6-methyl-2,3-dihydro-1,4-dioxine derivatives are formed as the major products (yield 70-99%) in the presence of t-BuOK in aprotic media (toluene, THF, DMSO) or in the absence of a solvent as a result of prototropic isomerization followed by intramolecular heterocyclization. Intramolecular nucleophilic cyclization of 3-(2-propynyloxy)propan-2-ols to 6-methylene-1,4-dioxane is the predominant process in water in the presence of KOH. In all cases, the fraction of 2,3-dihydro-5H-1,4-dioxepine derivatives among the cyclization products ranges from 0 to 5% (KOH) or to 14% (t-BuOK). * For communication XXI, see [1]. Base-catalyzed intramolecular cyclizations of -(2-propynyloxy)-[2-8], -(2-propynylsulfanyl)-[9], and -(2-propynylamino)alkan-1-ols [10,11], as well as of their 2-haloallyl analogs [4,5,9], have been studied in sufficient detail. Such cyclizations (which involve intramolecular nucleophilic addition of functional group at the acetylenic triple bond) are among the most widespread reactions leading to five-, six-, or seven-membered heterocycles containing one or two heteroatoms (N, O, S) [8,12, 13]. However, in the series of -(2-propynyloxy)alkan-1-ols, only 2-(2-propynyloxy)ethanol and its simplest derivatives R 1 C CC(R 2 )(R 3 )OCH(R 4 )CH(R 5 )OH (R 1 = R 2 = R 3 = R 4 = R 5 = H [3, 4, 7]; R 1 = R 2 = R 3 = R 4 = H, R 5 = Me, Ph; R 1 = R 2 = R 3 = R 5 = H, R 4 = Ph; R 1 = R 2 = R 3 = H, R 4 = R 5 = Me [3, 6]; R 1 = R 2 = R 4 = R 5 = H, R 3 = Me [7]; R 1 = R 4 = R 5 = H, R 2 = Me, R 3 = Ph [8]; R 1 = R 2 = R 4 = H, R 3 = R 5 = Me [3, 6, 7]; R 1 = Me, R 2 = R 3 = R 4 = R 5 = H [7]), 3-(2-propynyloxy)propan-1-ol [5], 2-(2-propynyloxy)cyclopentanol [7], and 2-(2-propynyloxy)cyclohexanol [3, 6, 7] were studied.Obviously, introduction of additional reaction centers, e.g., olefinic fragments with qualitatively different chemical natures of the double carbon-carbon bonds (specifically vinyloxy and allyloxy groups), into (2-propynyloxy)alkanol molecules should strongly extend the synthetic potential of both initial alkanols [1][2][3][4][5][6][7][8]12] and their cyclization products [1,8,14], as well as the range of their useful properties and the scope of practical application. Known representatives of this class of compounds are used in various fields (see, e.g., references in [1]), including the synthesis of dendrimers, dienes, -hydroxy and -oxo acids, -hydroxymethyl ketones, , '-dihy...

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confidence: 81%

Section: Iia-viiia Iic-viiicmentioning

confidence: 99%

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confidence: 95%

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Vinyl Ethers Containing an Epoxy Group: XXII. Synthesis and Base-Catalyzed Transformations of 1-(Allyloxy)- and 1-[2-(Vinyloxy)ethoxy]-3-(2-propynyloxy)propan-2-ols

et al. 2005

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“…24 Presumably, sodium forms a less stable intermediate five-membered chelate ring as compared to potassium used in the reference studies. The difference in isomerization activity of sodium and potassium alkoxides was noticed earlier, 29 however this comparison could not be considered valid as different alkoxides (potassium tert -butoxide and sodium methoxide) were used.…”

Section: Resultsmentioning

confidence: 94%

Synthesis of 5-substituted derivatives of isophthalic acid as non-polymeric amphiphilic coating for metal oxide nanoparticles

Nilov¹,

Kucheryavy²,

Walker³

et al. 2014

Tetrahedron Letters

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In the course of development of novel capping ligands with variable steric factor, which will be used as an organic coating for metal oxide nanoparticles, a base-catalyzed nucleophilic oxirane ring-opening addition reaction between dimethyl 5-hydroxyisophthalate and allyl glycidyl ether was studied. The allyl-terminated 1-1, 1-2 and 1-3 adducts and dihydroxylated derivative of the 1-1 adduct, 5-diglyceroxy isophthalic acid, were synthesized. The latter binds to the surface of 5 nm γ-Fe2O3 nanoparticles in reaction with their surfactant-free diethylene glycol colloids.

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“…The TBDPS-protected (furyl-2Ј)-glycol (17) was alkylated with allyl bromide and then the ether 19 was desilylated to give the alcohol 20. Subsequently, the (Z)-propenyl ether 21 was obtained from 20 by the rearrangement in the presence of t-BuOK in DMSO [21]. The free hydroxyl group in 21 was sulfonylated with TIBSCl to afford 22, using the same methodology as used for the preparation of 18 (Scheme 2).…”

Section: Synthesismentioning

confidence: 99%

Synthesis of 3-Substituted-clavams: Antifungal Properties, DD-Peptidase and β-Lactamase Inhibition

et al. 2007

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The Rearrangement of Allyl Ethers to Propenyl Ethers

Cited by 104 publications

References 0 publications

Vinyl Ethers Containing an Epoxy Group: XXII. Synthesis and Base-Catalyzed Transformations of 1-(Allyloxy)- and 1-[2-(Vinyloxy)ethoxy]-3-(2-propynyloxy)propan-2-ols

Vinyl Ethers Containing an Epoxy Group: XXII. Synthesis and Base-Catalyzed Transformations of 1-(Allyloxy)- and 1-[2-(Vinyloxy)ethoxy]-3-(2-propynyloxy)propan-2-ols

Synthesis of 5-substituted derivatives of isophthalic acid as non-polymeric amphiphilic coating for metal oxide nanoparticles

Synthesis of 3-Substituted-clavams: Antifungal Properties, DD-Peptidase and β-Lactamase Inhibition

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