Regioselectivity of the ring opening in the reaction of phenyloxirane, (phenylmethyl)oxirane and (2-phenylethyl)oxirane with K−, K+(15-crown-5)2

Grobelny, Zbigniew; Stolarzewicz, Andrzej; Morejko-Buż, Barbara; Maercker, Adalbert; Stanisław,; Krompiec, Stanisław; Bieg, Tadeusz

doi:10.1016/s0022-328x(03)00138-4

Cited by 14 publications

(15 citation statements)

References 22 publications

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“…The epoxy ring opened at the side of the most hydrogenized carbon affording compounds with a secondary hydroxy group [41]. These results are in agreement with our [1,37,38] and other published data [10,42] showing that the basecatalyzed opening of the oxirane ring occurs as a rule with the attack of the nucleophile on the least substituted carbon atom (b-opening); in the terminal oxiranes this is the methylene carbon atom (cleavage of the OCH 2 bond).…”

supporting

confidence: 91%

Vinyl Ethers Containing an Epoxy Group: XXIII. Reactions of Alkynylmagnesium Bromides with Glycidol Ethers: Synthesis and Thermal Transformations of 1-[2-( Vinyloxy)ethoxy]- and 1-(Allyloxy)-5-hexyn-2-ols, -5-phenyl-4-pentyn-2-ols, and -3-bromo-2-propanols

et al. 2005

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Reaction of 2-[2-(vinyloxy)ethoxy]methyl-and 2-(allyloxymethyl)oxiranes with 2-propynyl-and phenylethynylmagnesium bromides (1055°C, 0.54 h) resulted in new representatives of the series of 1-organyloxy-5-hexyn-2-ols, -5-phenyl-4-pentyn-2-ols, and -3-bromo-2-propanols in 5099% yields. During distillation the 1-[2-(vinyloxy)ethoxy]-5-phenyl-4-pentyn-2-ol and -3-bromo-2-propanol transform respectively into 2-methyl-4-(3-phenyl-2-propynyl)-and 2-methyl-4-(bromomethyl)-1,3,6-trioxocanes via intramolecular cyclization involving the hydroxy and vinyloxy groups.The reaction of organomagnesium compounds (Grignard [2, 3] and Iotsich reagents [3,4]) with oxiranes is a classical building up method of alcohol synthesis (with formation of a CC bond) [3, 511], also used for acetylene and allene alcohols [611]. The best studied reaction is that of the Grignard reagents with the simplest epoxides: unsubstituted oxirane, methyl-, phenyl-, 2,2-dimethyl-, and 2,3-dimethyloxiranes, although other examples of this process are also described (with naturally occurring epoxides, epoxyalcohols, epoxyketones, epoxyesters, diepoxides etc.) [511]. The reaction finds an industrial application in production of various technically important alcohols, in particular, those used in fragrance industry: 2-phenyl-1-ethanol (rose oil) [12], 3-phenyl-1-propanol (with the hyacinth fragrance) [13], 3,7-dimethyl-6-octen-1-ol (rhodinol) with a rose scent [14], alcohols with the properties of sex attractants and plant growth regulators. [15].The preparation was reported of chiral homoallyl alcohols in reaction of vinylmagnesium halides with glycidol derivatives containing as protection functions benzyl, methoxtphenylmethyl, tert-butyldimethylsilyl, and tertbutyldiphenylsilyl groups [16]. (R)-1-(Benzyloxy)-5-hexen-2-ol, the key intermediate in the stereoselective synthesis of trans-2,5-dioxymethylpyrrolidone derivatives possessing C 2 -symmetry, was obtained by treating with allylmagnesium chloride the optically active (S)-2-[(benzyloxy)methyl]oxirane [17]; reactions were performed of 2-(methoxymethyl)-and 2-(phenoxymethyl)-oxiranes with ethyl-and phenylmagnesium bromides [18]. Alkynols and allenols originate from both reactions of alkynylmagnesium halides with oxiranes [610] and of 2-ethynyloxiranes with Grignard reagents 11]. The alkynols combining the properties of the three most important classes of organic compounds (alcohols [19], acetylenes [20], and CH-acids when the compounds contained fragments CºCH and/or CH 2 CºC [21,22]) are valuable intermediates in preparation of a lot of synthetically and commercially significant products (chemicals for agriculture, drugs, and fragrant substances [9,23]). They are widely used in the synthesis of functionalized acetylene alcohols and diols [1, 24], heterocycles, including derivatives of furan [25], pyran [26], pyrrole [27], indole [28], pyrazole [29], 2,3-dihydropyridine, pyridine [30], benzazepine-1,5-dione [31], thiophene [32], various allene systems [20, 23, 24, 33], in particular, allenols that ar...

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supporting

confidence: 91%

Vinyl Ethers Containing an Epoxy Group: XXIII. Reactions of Alkynylmagnesium Bromides with Glycidol Ethers: Synthesis and Thermal Transformations of 1-[2-( Vinyloxy)ethoxy]- and 1-(Allyloxy)-5-hexyn-2-ols, -5-phenyl-4-pentyn-2-ols, and -3-bromo-2-propanols

et al. 2005

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“…Then, it was found that the regioselective cleavage of the alkyl-oxygen bond occurred also in methyl phenyl ether, ethyl phenyl ether [2], and allyl phenyl ether [3] in their reactions with K À , K þ (15-crown-5) 2 1. It was shown in further works that various cyclic ethers as monosubstituted oxiranes [3][4][5][6][7][8][9], oxetane [10][11][12] and tetrahydrofuran [13,14] can also be opened by alkalides. The most interesting seemed to be the reaction involving oxiranes.…”

Section: Introductionmentioning

confidence: 99%

“…The most interesting seemed to be the reaction involving oxiranes. The oxacyclic ring was opened in the a- [8,9] or in the b-position [3][4][5][6]9], i.e. between the substituted carbon atom and oxygen or between the CH 2 group and oxygen, respectively.…”

Section: Introductionmentioning

confidence: 99%

Decomposition of vinyl ethers by alkalide K−, K+(15-crown-5)2 via organopotassium intermediates

Grobelny

Stolarzewicz

Maercker

et al. 2004

Journal of Organometallic Chemistry

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“…To the best of our knowledge, there is no precedent report concerning these six- spectroscopic and microanalytical data with those of reported 2a. These complexes serve as potential Lewis acid catalysts for ring opening reactions of oxiranes, on which efforts to obtain efficient catalysts for the reaction have been devoted [7][8][9][10][11]. The utilization of zirconium b-diketonate of 2a as a catalyst precursor for synthesizing primary methoxypropanol was reported previously by our group [6].…”

Section: Introductionmentioning

confidence: 99%

Studies on tris(β-diketonato)zirconium (IV); syntheses, characterization and catalytic activity for ring opening of oxiranes

Permana¹,

Shimazu²,

Ichikuni³

et al. 2005

Catalysis Communications

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Regioselectivity of the ring opening in the reaction of phenyloxirane, (phenylmethyl)oxirane and (2-phenylethyl)oxirane with K−, K+(15-crown-5)2

Cited by 14 publications

References 22 publications

Vinyl Ethers Containing an Epoxy Group: XXIII. Reactions of Alkynylmagnesium Bromides with Glycidol Ethers: Synthesis and Thermal Transformations of 1-[2-( Vinyloxy)ethoxy]- and 1-(Allyloxy)-5-hexyn-2-ols, -5-phenyl-4-pentyn-2-ols, and -3-bromo-2-propanols

Vinyl Ethers Containing an Epoxy Group: XXIII. Reactions of Alkynylmagnesium Bromides with Glycidol Ethers: Synthesis and Thermal Transformations of 1-[2-( Vinyloxy)ethoxy]- and 1-(Allyloxy)-5-hexyn-2-ols, -5-phenyl-4-pentyn-2-ols, and -3-bromo-2-propanols

Decomposition of vinyl ethers by alkalide K−, K+(15-crown-5)2 via organopotassium intermediates

Studies on tris(β-diketonato)zirconium (IV); syntheses, characterization and catalytic activity for ring opening of oxiranes

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