{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,29]],"date-time":"2025-10-29T11:14:16Z","timestamp":1761736456791,"version":"build-2065373602"},"reference-count":47,"publisher":"MDPI AG","issue":"21","license":[{"start":{"date-parts":[[2025,10,28]],"date-time":"2025-10-28T00:00:00Z","timestamp":1761609600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>An excellent regioselectivity of vapor-phase catalytic transfer hydrogenation (CTH) of substituted oxiranes (methyl-, n-butyl-, and phenyloxirane) with alkanols (EtOH, 2-PrOH or 2-PeOH) as hydrogen donors in the presence of magnesium oxide as a catalyst was attained. In the vapor phase, all of these oxiranes as well as 1,2-epoxycyclohexane were hydrogenated. Moreover, it was found that primary alcohols were always the main products of CTH of methyl-, n-butyl-, and phenyloxirane with very good regioselectivity towards the alcohols: 93, 73, and 100%, respectively. It was shown that vapor-phase CTH of methyloxirane with 2-pentanol led to three products, two regioisomeric propanols, (1-PrOH and 2-PrOH), and also 1-(2-pentyloxy)-2-propanol. Their yields were 48%, 4%, and 35%, respectively. Two regioisomeric hexanols (1-HeOH, 54% yield and 2-HeOH, 20% yield) and 2-hexanone (14% yield) were found as products of the CTH of n-butyloxirane with 2-propanol as the hydrogen donor. For vapor-phase CTH of phenyloxirane, only 2-phenylethanol (95% yield) was observed together with minor amounts of phenylacetaldehyde. In vapor-phase CTH of 1,2-epoxycyclohexane, the presence of the transfer hydrogenation products (2-cyclohexenone, cyclohexanol, and cyclopentylmethanol) as well as isomerization products (cyclohexanone, 2-cyclohexenol, and 3-cyclohexenol) were found. It was noted that at 623 K, the yields of the former products were 18, 22, and 14%, respectively. Liquid-phase CTH of n-butyl- or phenyloxirane with 2-pentanol (b.p. 392 K) was unsuccessful.<\/jats:p>","DOI":"10.3390\/molecules30214212","type":"journal-article","created":{"date-parts":[[2025,10,29]],"date-time":"2025-10-29T04:26:29Z","timestamp":1761711989000},"page":"4212","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Regioselective Transfer Hydrogenation of Substituted Oxiranes with Alcohols Using MgO as the Catalyst"],"prefix":"10.3390","volume":"30","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-9631-8061","authenticated-orcid":false,"given":"Marek","family":"Gli\u0144ski","sequence":"first","affiliation":[{"name":"Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00664 Warsaw, Poland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Patrycja","family":"Waniek","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00664 Warsaw, Poland"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2025,10,28]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","unstructured":"Taleb, B., Jahjah, R., Cornu, D., Bechelany, M., Al Ajami, M., Kataya, G., Hijazi, A., and El-Dakdouki, M.H. (2023). Exploring Sources in Catalytic Transfer Hydrogenation: A Review of Unsaturated Compound Reduction. Molecules, 28.","DOI":"10.3390\/molecules28227541"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"670","DOI":"10.1039\/D0GC03931D","article-title":"Recent advances in heterogeneous catalytic transfer hydrogenation\/hydrogenolysis for valorization of biomass-derived furanic compounds","volume":"23","author":"Fanga","year":"2021","journal-title":"Green Chem."},{"key":"ref_3","doi-asserted-by":"crossref","unstructured":"Iwanek, E.M., Kirk, D.W., Gli\u0144ski, M., and Kaszkur, Z. (2023). Catalytic Transfer Hydrogenation Performance of Magnesium-Doped ZrO2 Solid Solutions. Catalysts, 13.","DOI":"10.3390\/catal13091229"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"1071","DOI":"10.1021\/acscatal.0c04939","article-title":"Recent Advances in Catalytic Transfer Hydrogenation with Formic Acid over Heterogeneous Transition Metal Catalysts","volume":"11","author":"Nie","year":"2021","journal-title":"ACS Catal."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"7274","DOI":"10.1002\/chem.201202836","article-title":"Enantioselective Synthesis of Alcohols and Amines by Iridium-Catalyzed Hydrogenation, Transfer Hydrogenation, and Related Processes","volume":"19","author":"Bartoszewicz","year":"2013","journal-title":"Chem. Eur. J."},{"key":"ref_6","doi-asserted-by":"crossref","unstructured":"Bar\u00e1th, E. (2018). Hydrogen Transfer Reactions of Carbonyls, Alkynes, and Alkenes with Noble Metals in the Presence of Alcohols\/Ethers and Amines as Hydrogen Donors. Catalysts, 8.","DOI":"10.3390\/catal8120671"},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"10304","DOI":"10.1039\/c1dt10544b","article-title":"The development of aqueous transfer hydrogenation catalysts","volume":"40","author":"Robertson","year":"2011","journal-title":"Dalton Trans."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"6621","DOI":"10.1021\/acs.chemrev.5b00203","article-title":"The Golden Age of Transfer Hydrogenation","volume":"115","author":"Wang","year":"2015","journal-title":"Chem. Rev."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"1113","DOI":"10.2174\/138527207781662500","article-title":"Heterogeneous Catalysis in the Meerwein-Ponndorf-Verley Reduction of Carbonyl Compounds","volume":"11","author":"Ruiz","year":"2007","journal-title":"Curr. Org. Chem."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"567","DOI":"10.1021\/cr60291a003","article-title":"Catalytic transfer hydrogenation","volume":"74","author":"Brieger","year":"1974","journal-title":"Chem. Rev."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"129","DOI":"10.1021\/cr00066a003","article-title":"Heterogeneous catalytic transfer hydrogenation and its relation to other methods for reduction of organic compounds","volume":"85","author":"Johnstone","year":"1985","journal-title":"Chem. Rev."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"1639","DOI":"10.2174\/138527206778249621","article-title":"Meerwein-Ponndorf-Verley Reduction over Heterogeneous Catalysts","volume":"10","author":"Chuah","year":"2006","journal-title":"Curr. Org. Chem."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"4665","DOI":"10.1021\/ol0358509","article-title":"Recyclable Polyurea-Microencapsulated Pd(0) Nanoparticles:\u2009 An Efficient Catalyst for Hydrogenolysis of Epoxides","volume":"5","author":"Ley","year":"2003","journal-title":"Org. Lett."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"13659","DOI":"10.1021\/acscatal.0c03294","article-title":"Erbium-Catalyzed Regioselective Isomerization\u2013Cobalt-Catalyzed Transfer Hydrogenation Sequence for the Synthesis of Anti-Markovnikov Alcohols from Epoxides under Mild Conditions","volume":"10","author":"Liu","year":"2020","journal-title":"ACS Catal."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"133","DOI":"10.1016\/j.apcata.2008.07.018","article-title":"Catalytic hydrogen transfer over magnesia. Vapour and liquid phase reduction of various aralkyl ketones","volume":"349","year":"2008","journal-title":"Appl. Catal. A Gen."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"131","DOI":"10.1016\/j.apcata.2015.11.046","article-title":"Vapour phase transfer hydrogenation of \u03b1,\u03b2-unsaturated carbonyl compounds. Thermodynamic and experimental studies","volume":"511","author":"Ulkowska","year":"2016","journal-title":"Appl. Catal. A Gen."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"117","DOI":"10.1016\/j.apcata.2018.02.001","article-title":"Description of the structure-chemoselectivity relationship in the transfer hydrogenation of \u03b1,\u03b2-unsaturated aldehydes and ketones with alcohols in the presence of magnesium oxide","volume":"554","author":"Ulkowska","year":"2018","journal-title":"Appl. Catal. A Gen."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"293","DOI":"10.1007\/s10562-010-0497-7","article-title":"Reactivity of Alcohols in Chemoselective Transfer Hydrogenation of Acrolein over Magnesium Oxide as the Catalyst","volume":"141","author":"Ulkowska","year":"2011","journal-title":"Catal. Lett."},{"key":"ref_19","doi-asserted-by":"crossref","unstructured":"Gli\u0144ski, M., Dubinin, O., Rostek, K., and Waniek, P. (2025). Chemoselective Transfer Hydrogenation over MgO as the Catalyst: Acetylnaphthalenes, Diacylbenzenes, Acetophenone, Benzaldehyde, and Various Aliphatic Ketones as Hydrogen Acceptors. Reactions, 6.","DOI":"10.3390\/reactions6010004"},{"key":"ref_20","doi-asserted-by":"crossref","unstructured":"Gli\u0144ski, M., Ulkowska, U., Kaszkur, Z., \u0141omot, D., and Winiarek, P. (2024). MgO Modified by X2, HX, or Alkyl Halide (X = Cl, Br, or I) Catalytic Systems and Their Activity in Chemoselective Transfer Hydrogenation of Acrolein into Allyl Alcohol. Molecules, 29.","DOI":"10.3390\/molecules29133180"},{"key":"ref_21","doi-asserted-by":"crossref","unstructured":"Gli\u0144ski, M., Armusiewicz, D., \u0141ukasik-Kwa\u015bniewska, K., Materowski, M., Ru\u0142ka, A., Iwanek, E.M., and Kucharska, M. (2025). Diastereoselective Transfer Hydrogenation of Cyclic and Bicyclic Ketones over Selected Metal Oxides as Catalysts. Molecules, 30.","DOI":"10.3390\/molecules30102153"},{"key":"ref_22","unstructured":"Weissemel, K., and Arpe, H.-J. (2008). Industrial Organic Chemistry, Wiley-VCH. [4th ed.]."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"3743","DOI":"10.1021\/ja512389y","article-title":"Chemoselective Hydrogenation of Carbonyl Compounds and Acceptorless Dehydrogenative Coupling of Alcohols","volume":"137","author":"Spasyuk","year":"2015","journal-title":"J. Am. Chem. Soc."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"5203","DOI":"10.1021\/acs.organomet.5b00824","article-title":"A Single Nickel Catalyst for the Acceptorless Dehydrogenation of Alcohols and Hydrogenation of Carbonyl Compounds","volume":"34","author":"Chakraborty","year":"2015","journal-title":"Organometallics"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"2274","DOI":"10.1021\/acs.joc.7b03174","article-title":"Cp*Ir(2,2\u2033-bpyO)(H2O)] is a highly efficient and general catalyst for transfer hydrogenation of carbonyl compounds and chemoselective transfer hydrogenation of unsaturated aldehydes with isopropanol under neutral conditions","volume":"83","author":"Wang","year":"2018","journal-title":"J. Org. Chem."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"8376","DOI":"10.1021\/acs.joc.4c00145","article-title":"Iron(III) salen complexes catalyze selective hydroborations of ketones and unactivated imines with pinacolborane in the absence of any additive","volume":"89","author":"Latha","year":"2024","journal-title":"J. Org. Chem."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"7625","DOI":"10.1016\/S0040-4020(01)88286-7","article-title":"Oxirane ring-opening with alcohol catalyzed by organotin phosphate condensates","volume":"47","author":"Otera","year":"1991","journal-title":"Tetrahedron"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"e202400380","DOI":"10.1002\/cctc.202400380","article-title":"Regioselective Ring Opening of Epoxide with Alcohols: A Selective Route to \u03b1-Alkylated Ketones and \u03b2-Alkylated Secondary Alcohols","volume":"16","author":"Nandi","year":"2024","journal-title":"ChemCatChem"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"1382","DOI":"10.1021\/acs.orglett.3c04304","article-title":"A readily available Ti catalyst carries out the anti-Markovnikov reduction of a wide range of epoxides under mild conditions in the presence of [BH4]\u2212 as both the electron and the hydrogen atom source","volume":"26","author":"Li","year":"2024","journal-title":"Org. Lett."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"9774","DOI":"10.1021\/acs.orglett.9b03995","article-title":"Ruthenium-Catalyzed Selective Hydrogenation of Epoxides to Secondary Alcohols","volume":"21","author":"Thiyagarajan","year":"2019","journal-title":"Org. Lett."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"1813","DOI":"10.1246\/bcsj.60.1813","article-title":"Chemo- and Regioselective Reduction of Epoxides with Sodium Borohydride in Mixed Solvent Containing Methanol","volume":"60","author":"Ookawa","year":"1987","journal-title":"Bull. Chem. Soc. Jpn."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"13100","DOI":"10.1039\/D4RA01834F","article-title":"Exploring the synthetic potential of epoxide ring opening reactions toward the synthesis of alkaloids and terpenoids: A review","volume":"14","author":"Hanif","year":"2024","journal-title":"RSC Adv."},{"key":"ref_33","first-page":"1581","article-title":"Reduction of epoxy isophorone oxime by metal hydrides","volume":"74","author":"Dresler","year":"2000","journal-title":"Pol. J. Chem."},{"key":"ref_34","doi-asserted-by":"crossref","unstructured":"Lewandowski, D., and Hreczycho, G. (2024). Cobalt-Catalyzed Reduction of Aldehydes to Alcohols via the Hydroboration Reaction. Int. J. Mol. Sci., 25.","DOI":"10.3390\/ijms25147894"},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"8153","DOI":"10.1021\/cr500036t","article-title":"The Chemistry of Transition Metals with Three-Membered Ring Heterocycles","volume":"114","author":"Huang","year":"2014","journal-title":"Chem. Rev."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"3020","DOI":"10.1039\/C9CY00791A","article-title":"Iridium-promoted conversion of terminal epoxides to primary alcohols under acidic conditions using hydrogen","volume":"9","author":"Rainsbury","year":"2019","journal-title":"Catal. Sci Technol."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"e202200118","DOI":"10.1002\/asia.202200118","article-title":"Catalytic Hydrogenation of Epoxides to Alcohols","volume":"17","author":"Thiyagarajan","year":"2022","journal-title":"Chem. Asian J."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"523","DOI":"10.1038\/s41929-019-0286-7","article-title":"Iron-catalyzed regioselective hydrogenation of terminal epoxides to alcohols under mild conditions","volume":"2","author":"Liu","year":"2019","journal-title":"Nat. Catal."},{"key":"ref_39","doi-asserted-by":"crossref","unstructured":"Sajiki, H., Hattori, K., and Hirota, K. (1999). Pd\/C(en)-catalyzed regioselective hydrogenolysis of terminal epoxides to secondary alcohols. Chem. Commun., 1041\u20131042.","DOI":"10.1039\/a902213i"},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"3417","DOI":"10.1021\/ol701456w","article-title":"Magnetically Separable Pd Catalyst for Highly Selective Epoxide Hydrogenolysis under Mild Conditions","volume":"8","author":"Kwon","year":"2007","journal-title":"Org. Lett."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"326","DOI":"10.1039\/b616486b","article-title":"Palladium nanoparticles-catalyzed regio- and chemoselective hydrogenolysis of benzylic epoxides in water","volume":"9","author":"Thiery","year":"2007","journal-title":"Green Chem."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"261","DOI":"10.1016\/j.jcat.2021.02.027","article-title":"Selective palladium nanoparticles-catalyzed hydrogenolysis of industrially targeted epoxides in water","volume":"396","author":"Duval","year":"2021","journal-title":"J. Catal."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"4190","DOI":"10.1021\/om034006j","article-title":"Highly Efficient Chemoselective Hydrogenolysis of Epoxides Catalyzed by a (\u03b75-C5(CH3)5)Ru Complex Bearing a 2-(Diphenylphosphino)ethylamine Ligand","volume":"22","author":"Ito","year":"2003","journal-title":"Organometallics"},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"11321","DOI":"10.1002\/anie.202002844","article-title":"A General Regioselective Synthesis of Alcohols by Cobalt-Catalyzed Hydrogenation of Epoxides","volume":"59","author":"Liu","year":"2020","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_45","doi-asserted-by":"crossref","unstructured":"Gli\u0144ski, M., Czajka, A., Ulkowska, U., Iwanek, E.M., \u0141omot, D., and Kaszkur, Z. (2022). A Hands-on Guide to the Synthesis of High-Purity and High-Surface-Area Magnesium Oxide. Catalysts, 12.","DOI":"10.3390\/catal12121595"},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"680","DOI":"10.1021\/ja01208a047","article-title":"The reaction of Propylene Oxide with Alcohols","volume":"68","author":"Chitwood","year":"1946","journal-title":"J. Am. Chem. Soc."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"2730","DOI":"10.1139\/v74-398","article-title":"Isomeric Mixture Analysis of Some Ring-opening Reactions of Styrene Oxide","volume":"52","author":"Hocking","year":"1974","journal-title":"Can. J. Chem."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/30\/21\/4212\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,29]],"date-time":"2025-10-29T04:28:23Z","timestamp":1761712103000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/30\/21\/4212"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,10,28]]},"references-count":47,"journal-issue":{"issue":"21","published-online":{"date-parts":[[2025,11]]}},"alternative-id":["molecules30214212"],"URL":"https:\/\/doi.org\/10.3390\/molecules30214212","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2025,10,28]]}}}