- ZnAlMCM-41: a very ecofriendly and reusable solid acid catalyst for the highly selective synthesis of 1,3-dioxanes by the Prins cyclization of olefins
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The Prins cyclization of styrene (SE) with paraformaldehyde (PFCHO) was conducted with mesoporous ZnAlMCM-41 catalysts for the synthesis of 4-phenyl-1,3-dioxane (4-PDO) using a liquid phase heterogeneous catalytic method. For a comparison study, the Prins cyclization reaction was also conducted over different nanoporous catalysts,e.g.mesoporous solid acid catalysts, AlMCM-41(21) and ZnMCM-41(21), and microporous catalysts, USY, Hβ, HZSM-5, and H-mordenite. The recyclable mesoporous ZnAlMCM-41 catalysts were reused in this reaction to evaluate their catalytic stabilities. Since ZnAlMCM-41(75) has higher catalytic activity than other solid acid catalysts, washed ZnAlMCM-41(75)/W-ZnAlMCM-41(75) was prepared using an efficient chemical treatment method and used with various reaction parameters to find an optimal parameter for the highly selective synthesis of 4-PDO. W-ZnAlMCM-41(75) was also used in the Prins cyclization of olefins with PFCHO and formalin (FN, 37% aqueous solution of formaldehyde (FCHO)) under different reaction conditions to obtain 1,3-dioxanes, which are widely used as solvents or intermediates in organic synthesis. Based on the nature of catalysts used under different reaction conditions, a reasonable plausible reaction mechanism for the Prins cyclization of SE with PFCHO is proposed. Notably, it can be seen from the catalytic results of all catalysts that the W-ZnAlMCM-41(75) catalyst has higher 4-PDO selectivity with exceptional catalytic activity than other microporous and mesoporous catalysts.
- Selvaraj, Manickam,Assiri, Mohammed A.,Singh, Hari,Appaturi, Jimmy Nelson,Subrahmanyam, Ch.,Ha, Chang-Sik
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p. 1672 - 1682
(2021/02/16)
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- The Catalytic Asymmetric Intermolecular Prins Reaction
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Despite their significant potential, catalytic asymmetric reactions of olefins with formaldehyde are rare and metal-free approaches have not been previously disclosed. Here we describe an enantioselective intermolecular Prins reaction of styrenes and paraformaldehyde to form 1,3-dioxanes, using confined imino-imidodiphosphate (iIDP) Br?nsted acid catalysts. Isotope labeling experiments and computations suggest a concerted, highly asynchronous addition of an acid-activated formaldehyde oligomer to the olefin. The enantioenriched 1,3-dioxanes can be transformed into the corresponding optically active 1,3-diols, which are valuable synthetic building blocks.
- Diáz-Oviedo, C. David,Maji, Rajat,List, Benjamin
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supporting information
p. 20598 - 20604
(2021/12/14)
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- Chemoselective Deoxygenation of 2° Benzylic Alcohols through a Sequence of Formylation and B(C6F5)3-Catalyzed Reduction
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A sequence of formylation and B(C6F5)3-catalyzed reduction of the resulting formate with Et3SiH enables the chemoselective deoxygenation of secondary benzylic alcohols. Primary benzylic and tertiary non-benzylic alcohols are not reduced by this protocol. The formyl group fulfills a double role as activator and self-sacrificing protecting group. The deoxygenation of these formates is fast and can be carried out in the presence of other potentially reducible groups. Neighboring-group participation was found in the deoxygenation of certain diol motifs.
- Oestreich, Martin,Richter, Sven C.
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supporting information
p. 2103 - 2106
(2021/07/22)
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- Synthesis of ethers and cyclic acetals in the presence of CBV-720 zeolite
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СBV-720 zeolite was compared to H-Beta zeolite and KU-2 cation-exchange resin in the catalytic performance in addition of alcohols to norbornene, in condensation of aldehyde and ketone with di- and triols, and in the Prins reaction of olefins with formaldehyde. These reactions, when performed on СBV-720 zeolite, occur 1.5–2 times faster than on the other catalysts. The corresponding ethers and cyclic acetals were synthesized.
- Baiburtli,Raskil’dina,Zlotskii
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p. 1098 - 1101
(2017/11/22)
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- Highly efficient synthesis of 1,3-dioxanes via prins reaction in bronsted-acidic imidazolium ionic liquid
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The high-yielding synthesis of a wide variety of 1,3-dioxanes via the Prins reaction under mild conditions has been demonstrated using Bronsted- acidic imidazolium ionic liquid [bmim(SO3H)][OTf] or bmimOTf. The use of ionic liquid makes this synthesis simple, convenient, cost-effective, and environmentally friendly. Furthermore, bmimOTf was conveniently separated from the products and can be easily recycled for the Prins reaction with excellent yields. This method works well with a variety of aliphatic aldehydes including formaldehyde, acetaldehyde, propionaldehyde, and cyclohexanecarboxaldehyde. [Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications for the following free supplemental resource(s): Full experimental and spectral details.]
- Kalkhambkar, Rajesh G.,Jeong, Yeon T.
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p. 762 - 771
(2014/03/21)
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- Methylene acetal formation from 1,2- and 1,3-diols using an O, S -acetal, 1,3-dibromo-5,5-dimethylhydantoin, and BHT
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A mild and efficient method for formation of methylene acetals from 1,2- and 1,3-diols using methoxymethylphenylsulfide, 1,3-dibromo-5,5- dimethylhydantoin (DBDMH), and dibutylhydroxytoluene (BHT) is described. The use of BHT in this process suppresses side reactions and enables high-yielding formation of methylene acetals of various diols, including carbohydrate-type substrates.
- Maegawa, Tomohiro,Koutani, Yasuyuki,Otake, Kazuki,Fujioka, Hiromichi
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p. 3384 - 3390
(2013/06/26)
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- Prins cyclization of styrenes or acetophenone catalyzed by DBSA in water
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Dodecylbenzenesulfonic acid (DBSA) was proved to be an efficient catalyst for Prins cyclization of styrenes and formaldehyde or acetaldehyde in water. A tandem dehydration/ Prins cyclization reaction using a tertiary alcohol and formaldehyde as substrates proceeded very well by using DBSA as catalyst. Acetophenone, which is less reactive compared with styrene, can also react with formaldehyde when catalyzed by DBSA in water to afford 1,3-dioxan-5- ylphenylmethanone in good yield. Copyright Taylor & Francis Group, LLC.
- Zhang, Juan,Hua, Lin,Li, Feifei,Wu, Xuefen,Tian, Shengzhi,Yang, Jing
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experimental part
p. 1234 - 1242
(2012/04/04)
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- Investigation of Prins reaction for the synthesis of 2, 4-disubstituted tetrahydropyran derivatives and 1, 3-dioxanes using polyaniline supported acid as reusable catalyst
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The Prins cyclization of homoallyl alcohol with a variety of aldehydes were observed under reflux condition in dichloromethane using both polyaniline supported TsOH (PANI-TsOH) and FeCl3 (PANI- FeCl3) as reusable acid catalysts with the formation of 2,4-disubstituted tetrahydropyran ether as single product. In case of 4-, 3- and 2- nitro benzaldehydes, the reaction generated acetal of the aldehyde and homoallylic alcohol as single product. Additionally, both catalysts were investigated for the synthesis of 1, 3-dioxane in dichloromethane under reflux and at ambient temperature Indian Academy of Sciences.
- Borah, Kalyan Jyoti,Borah, Ruli
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experimental part
p. 623 - 630
(2012/07/14)
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- Iodine as a mild and versatile reagent for the synthesis of 1,3-dioxane derivatives via the Prins reaction
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Iodine is found to be an effective reagent for the cross-coupling of olefins with aldehydes under mild conditions to produce 4-substituted 1,3-dioxane derivatives in excellent yields and in short reaction times with high selectivity. The use of iodine makes this procedure simple, convenient, cost-effective and practical. This method works not only with formaldehyde but also with acetaldehyde, propionaldehyde and cyclohexanecarboxaldehyde.
- Yadav,Reddy, B.V. Subba,Hara Gopal,Narayana Kumar,Madavi,Kunwar
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p. 4420 - 4423
(2008/12/21)
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- Synthesis of 1,3-dioxanes catalyzed by TsOH-SiO2 under solvent-free conditions
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Silica-supported p-toluene sulfonic acid is found to be an excellent catalyst for the Prins reaction to produce 1,3-dioxanes in good yields from olefins and aliphatic aldehydes in dichloromethane at room temperature and solventless microwave irradiation within a short reaction time. Copyright Taylor & Francis Group, LLC.
- Borah, Kalyan Jyoti,Phukan, Mridula,Borah, Ruli
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p. 3082 - 3087
(2008/12/22)
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- Selectivity enhancement of silica-supported sulfonic acid catalysts in water by coating of ionic liquid
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Coating of silica-supported sulfonic acid catalysts with hydrophobic ionic liquid leads to a significant improvement of catalyst selectivity. Many organic reactions, including Prins cyclization, cycloaddition of epoxide to aldehyde, and dehydrative etherification of secondary benzyl alcohols, proceed well in formalin or pure water. In particular, tandem dehydration/Prins cyclization reactions of tertiary and secondary alcohols with formaldehyde were developed for the first time.
- Gu, Yanlong,Karam, Ayman,Jerome, Francois,Barrault, Joel
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p. 3145 - 3148
(2008/02/10)
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- Novel hydrophobic Bronsted acidic ionic-liquids as efficient and reusable catalysts for organic reactions in water
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Novel Hydrophobic Bronsted acidic ionic liquids (HBAIL) were prepared and utilized as acid catalysts in organic reactions in water. HBAILs were demonstrated, for the first time, to be effective catalysts for Prins cyclization of styrene derivatives in water with a formaldehyde water solution. Many styrene derivatives could be successfully converted to the corresponding 1,3-dioxanes. Other dehydration reactions also proceeded well using HBAILs in water. After reactions, HBAILs could be easily recovered and reused without significant loss of activity. Copyright
- Gu, Yanlong,Ogawa, Chikako,Kobayashi, Shu
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p. 1176 - 1177
(2007/10/03)
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- Facile and efficient method for the Prins reactions of styrenes and homoallyl alcohols to 1,3-dioxanes and 4-tetrahydropyranols using bismuth(III) triflate
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Bismuth(III) inflate has been found to be an efficient catalyst for the Prins reactions of styrenes and homoallyl alcohols, the reaction proceeds rapidly and affords the corresponding 1,3-dioxanes and tetrahydropyran-4-ol in good yields. Scope and limitations of the styrenes and homoallyl alcohols are reported. Copyright Taylor & Francis, Inc.
- Sreedhar,Swapna,Sridhar,Saileela,Sunitha
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p. 1177 - 1182
(2007/10/03)
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- Application of empirical and quantum-chemical computational methods in the determination of the free conformational energy of substituents in 1,3-dioxanes
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The advantages and disadvantages of empirical and quantum-chemical methods for the determination of the free conformational energy of methyl and phenyl substituents at the C(4) and C(5) atoms of the ring in the molecules of 1,3-dioxanes are analyzed.
- Kuznetsov,Alekseeva
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p. 713 - 720
(2007/10/03)
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- Selective Prins reaction of styrenes and formaldehyde catalyzed by 2,6-Di-tert-butylphenoxy(difluoro)borane
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The sterically congested Lewis acid 1 was used as a catalyst in the Prins reaction of various styrenes and formaldehyde. 4-Aryl-1,3-dioxanes 5 were selectively formed as the exclusive products of the reaction with styrenes 4a-i and vinylthiophenes 4j-k. The reaction proceeded in most cases with good to excellent yields (55-99%). Styrenes which carried a strongly electron-withdrawing group (CN, CO2Me) did not react. The reaction with β-alkylstyrenes 6 was successful for the methyl substituted substrate 6a and yielded (88%) trans-5-methyl-4-phenyl-1,3-dioxane (7a) preferentially (dr = 75:25). For steric reasons, other β-alkylstyrenes 6b-d did not react. The remarkable stereodiscrimination attained by catalyst 1 was employed in the regioselective transformation of 4-propenylstyrene (10) to dioxane 11 (83% yield).
- Bach, Thorsten,Loebel, Johannes
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p. 2521 - 2526
(2007/10/03)
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- Thermolysis of a spiro-fused oxadiazoline: The carbonyl ylide-cyclic carbene-diradical sequence
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Thermolysis of spiro-fused oxadiazoline 1 in benzene led to loss of N2 to form a carbonyl ylide intermediate. Most of the ylide fragmented to acetone and 4-phenyl-1,3-dioxane-2-ylidene, which could be trapped with tert-butyl alcohol. In the absence of the trapping agent, the major pathway followed by the carbene was fragmentation to a diradical, 5-phenyl-2-oxa-1-oxo-1,5-pentanediyl. The latter diradical coupled to α-phenyl-δ-butyrolactone and decarboxylated to afford cyclopropylbenzene. Other products from the reaction were those of apparent insertion of the carbene into a C-H bond of the benzene solvent and into a C-H bond of acetone. Such reactions appear to be without precedent - alternative, non-carbene mechanisms are proposed.
- Merkley, Nadine,Warkentin, John
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p. 1187 - 1195
(2007/10/03)
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- First TaCl5-SiO2 catalyzed prins reaction : Comparative study of conventional heating vs microwave irradiation
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TaCl5-SiO2 catalyzed Prins reaction has been achieved for the first time using microwave irradiation.
- Chandrasekhar,Subba Reddy
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p. 851 - 852
(2007/10/03)
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- Microwave Enhancement of the Prins Reaction
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The effect of microwave irradiation on the condensation of olefins with formaldehyde (Prins reaction) has been studied. The kinetic curves for accumulation of 4-phenyl-1,3-dioxane and 4-methyl-4-phenyl-1,3-dioxane suggest that the microwave-enhanced reactions are 2.4-2.6 times faster than those occurring on thermal heating.
- Zorin,Maslennikov,Shavshukova,Shakhova,Rakhmankulov
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p. 725 - 726
(2007/10/03)
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- Cation-Exchanged Montmorillonite (Mn+-Mont)-Catalyzed Prins Reaction
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The Prins reaction of styrenes with paraformaldehyde or 1,3,5-trioxane in toluene in the presence of cation-exchanged montmorillonite (Mn+-mont), which worked as a Bronsted acid catalyst, at 80°C produced 4-aryl-1,3-dioxanes selectively in up to 99% isolated yield with a turnover number of up to 5.9×102. Among the examined 21 Mn+-monts, Ce3+- and Fe3+-monts were revealed to be quite effective. Regeneration of the catalyst was confirmed with the Ce3+-mont, which could be effectively recycled at least three times. Many lanthanide metal ion-exchanged montmorillonites (Ln3+-monts) were prepared and characterized by X-ray powder diffraction (XRD) and temperature-programmed desorption of ammonia gas (NH3-TPD) methods.
- Tateiwa, Jun-Ichi,Hashimoto, Keiji,Yamauchi, Takayoshi,Uemura, Sakae
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p. 2361 - 2368
(2007/10/03)
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- THE PALLADIUM-CATALYZED ARYLATION OF 4-H-1,3-DIOXIN
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4H-1,3-Dioxin was firstly arylated by using Heck reaction, and the reaction in the presence of (R)-BINAP gave enantiomerically enriched 4-phenyldioxin which was converted into optically active 1-phenyl-1,3-propanediol.
- Sakamoto, Takao,Kondo, Yoshinori,Yamanaka, Hiroshi
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p. 6845 - 6848
(2007/10/02)
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- Ruthenium-catalysed Prins Reaction
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The reactions of dienes and alkenes with aldehydes and carboxylic acids leading to derivatives of 1,3-diols are catalysed by ruthenium salts under mild conditions; oxygenated compounds of higher molecular weight may also be produced by variations in the reaction conditions.
- Thivolle-Cazat, Jean,Tkatchenko, Igor
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p. 1128 - 1129
(2007/10/02)
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- SUR UN CONCEPT ORIGINAL : LA CATALYSE TRIPHASIQUE ET LES ECHANGEURS DE CATIONS
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The condensation in triphase process of aqueous formaldehyde with aromatic alkanes dissolved in an organic solvent is possible in the presence of polystyrene sulfonic acid resin.
- Delmas, Michel,Gaset, Antoine
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p. 723 - 724
(2007/10/02)
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