{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,17]],"date-time":"2026-08-17T14:41:41Z","timestamp":1786977701519,"version":"build-2736575974"},"reference-count":47,"publisher":"American Chemical Society (ACS)","issue":"6","license":[{"start":{"date-parts":[[2024,2,4]],"date-time":"2024-02-04T00:00:00Z","timestamp":1707004800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100000780","name":"European Commission","doi-asserted-by":"publisher","award":["LX22NPO5104"],"award-info":[{"award-number":["LX22NPO5104"]}],"id":[{"id":"10.13039\/501100000780","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100004240","name":"Akademie Ved Cesk? Republiky","doi-asserted-by":"publisher","award":["RVO 61388963"],"award-info":[{"award-number":["RVO 61388963"]}],"id":[{"id":"10.13039\/501100004240","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2024,2,13]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>The stereoselective reduction of the steroidal 4-ene-3-ketone moiety (enone) affords the 5\u03b2-steroid backbone that is a key structural element of biologically important neuroactive steroids. Neurosteroids have been currently studied as novel and potent central nervous system drug-like compounds for the treatment of, e.g., postpartum depression. As a green methodology, we studied the palladium-catalyzed hydrogenation of steroidal 4-ene-3-ketones in the presence of ionic liquids derived from natural carboxylic acids. The hydrogenation proceeds with improved 5\u03b2-selectivity in the presence of tetrabutylammonium carboxylates as additives compared to the exclusive use of an organic solvent. Under optimal conditions, using tetrabutylammonium d-mandelate, the reduction of testosterone led to 5\u03b2-dihydrotestosterone in high yield and stereoselectivity and no byproduct formation was observed. Moreover, the catalyst could be recycled. The presence of additional substituents on the steroid backbone showed a significant effect on the 5\u03b2-selectivity.<\/jats:p>","DOI":"10.1021\/acsomega.3c08963","type":"journal-article","created":{"date-parts":[[2024,2,4]],"date-time":"2024-02-04T12:52:06Z","timestamp":1707051126000},"page":"7043-7052","source":"Crossref","is-referenced-by-count":0,"title":["Stereoselective Reduction of Steroidal 4\u2011Ene-3-ketones\nin the Presence of Biomass-Derived Ionic Liquids Leading to Biologically\nImportant 5\u03b2-Steroids"],"prefix":"10.1021","volume":"9","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-8263-9884","authenticated-orcid":true,"given":"Eszter","family":"Sza\u0301nti-Pinte\u0301r","sequence":"first","affiliation":[{"name":"Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences , ,","place":["Prague, Czech Republic, 166 10"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lada","family":"Jirkalova\u0301","sequence":"additional","affiliation":[{"name":"Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences , ,","place":["Prague, Czech Republic, 166 10"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Radek","family":"Pohl","sequence":"additional","affiliation":[{"name":"Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences , ,","place":["Prague, Czech Republic, 166 10"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lucie","family":"Bedna\u0301rova\u0301","sequence":"additional","affiliation":[{"name":"Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences , ,","place":["Prague, Czech Republic, 166 10"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7131-5948","authenticated-orcid":true,"given":"Eva","family":"Kudova","sequence":"additional","affiliation":[{"name":"Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences , ,","place":["Prague, Czech Republic, 166 10"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2024,2,4]]},"reference":[{"issue":"5","key":"2026081709204643700_cit1","doi-asserted-by":"publisher","first-page":"3508","DOI":"10.1021\/cr1003248","article-title":"Room-Temperature Ionic Liquids: Solvents for Synthesis\nand Catalysis. 2","volume":"111","author":"Hallett","year":"2011","journal-title":"Chem. 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Rev."},{"issue":"21","key":"2026081709204643700_cit3","doi-asserted-by":"publisher","first-page":"5207","DOI":"10.3390\/molecules25215207","article-title":"Industrial Applications of Ionic\nLiquids","volume":"25","author":"Greer","year":"2020","journal-title":"Molecules"},{"issue":"4","key":"2026081709204643700_cit4","doi-asserted-by":"publisher","first-page":"185","DOI":"10.1039\/B419172B","article-title":"Toxicity and\nantimicrobial activity of imidazolium\nand pyridinium ionic liquids","volume":"7","author":"Docherty","year":"2005","journal-title":"Green Chem."},{"issue":"7","key":"2026081709204643700_cit5","doi-asserted-by":"publisher","first-page":"621","DOI":"10.1039\/b602161a","article-title":"Anion effects on the\ncytotoxicity\nof ionic liquids","volume":"8","author":"Stolte","year":"2006","journal-title":"Green Chem."},{"issue":"6","key":"2026081709204643700_cit6","doi-asserted-by":"publisher","first-page":"2917","DOI":"10.1021\/acssuschemeng.6b00553","article-title":"Biobased Ionic Liquids:\nSolvents for a Green Processing Industry?","volume":"4","author":"Hulsbosch","year":"2016","journal-title":"ACS\nSustainable Chem. Eng."},{"key":"2026081709204643700_cit7","doi-asserted-by":"publisher","first-page":"28","DOI":"10.1016\/j.cogsc.2016.09.001","article-title":"Amino acid based ionic\nliquids: A green and sustainable\nperspective","volume":"2","author":"Kirchhecker","year":"2016","journal-title":"Curr. Opin. Green Sustainable Chem."},{"issue":"10","key":"2026081709204643700_cit8","doi-asserted-by":"publisher","DOI":"10.1016\/j.heliyon.2020.e04974","article-title":"Lactic acid production\n- producing microorganisms and\nsubstrates sources-state of art","volume":"6","author":"Abedi","year":"2020","journal-title":"Heliyon"},{"issue":"30","key":"2026081709204643700_cit9","doi-asserted-by":"publisher","first-page":"6150","DOI":"10.1016\/j.tet.2013.05.054","article-title":"Biomass derived\nionic liquids: synthesis from natural organic acids, characterization,\ntoxicity, biodegradation and use as solvents for catalytic hydrogenation\nprocesses","volume":"69","author":"Ferlin","year":"2013","journal-title":"Tetrahedron"},{"issue":"114","key":"2026081709204643700_cit10","doi-asserted-by":"publisher","first-page":"113583","DOI":"10.1039\/C6RA23056C","article-title":"New biobased\ntetrabutylphosphonium ionic liquids: synthesis, characterization and\nuse as a solvent or co-solvent for mild and greener Pd-catalyzed hydrogenation\nprocesses","volume":"6","author":"Hayouni","year":"2016","journal-title":"RSC Adv."},{"issue":"23","key":"2026081709204643700_cit11","doi-asserted-by":"publisher","first-page":"3349","DOI":"10.1002\/pol.20200638","article-title":"Exploration of mandelic\nacid-based polymethacrylates:\nSynthesis, properties, and stereochemical effects","volume":"58","author":"Yarolimek","year":"2020","journal-title":"J. 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Med. Chem."},{"issue":"3","key":"2026081709204643700_cit29","doi-asserted-by":"publisher","first-page":"259","DOI":"10.1016\/0304-5102(90)80001-Y","article-title":"Enantioselective hydrogenation\nof isophorone","volume":"61","author":"Tungler","year":"1990","journal-title":"J. Mol. Catal."},{"issue":"12","key":"2026081709204643700_cit30","doi-asserted-by":"publisher","first-page":"1776","DOI":"10.3390\/cryst12121776","article-title":"Current Trends in Green\nSolvents: Biocompatible Ionic Liquids","volume":"12","author":"Tzani","year":"2022","journal-title":"Crystals"},{"issue":"1","key":"2026081709204643700_cit31","doi-asserted-by":"publisher","first-page":"231","DOI":"10.1021\/jo00800a059","article-title":"Stereochemistry of\nthe palladium-catalyzed hydrogenation of 3-oxo-4-ene steroids. III.\nEffects of the functional groups at C-11, C-17, and C-20 on the hydrogenation","volume":"36","author":"Mori","year":"1971","journal-title":"J. Org. Chem."},{"issue":"13","key":"2026081709204643700_cit32","doi-asserted-by":"publisher","first-page":"2729","DOI":"10.1021\/jo01301a043","article-title":"Highly stereoselective hydrogenation\nof 3-oxo-4-ene\nand \u22121,4-diene steroids to 5\u03b2 compounds with palladium\ncatalyst","volume":"45","author":"Tsuji","year":"1980","journal-title":"J. Org. Chem."},{"issue":"10","key":"2026081709204643700_cit33","doi-asserted-by":"publisher","first-page":"1528","DOI":"10.1135\/cccc19981528","article-title":"On steroids - Part CCCXCVII - Long-range\neffect of\n17-substituents in 3-oxo steroids on 4,5-double bond hydrogenation","volume":"63","author":"Sidova","year":"1998","journal-title":"Collect. Czech. Chem. Commun."},{"issue":"1","key":"2026081709204643700_cit34","doi-asserted-by":"publisher","first-page":"18","DOI":"10.1021\/acs.joc.2c00616","article-title":"Parts-Per-Million of Soluble Pd0\nCatalyze the Semi-Hydrogenation Reaction of Alkynes to Alkenes","volume":"88","author":"Ballesteros-Soberanas","year":"2023","journal-title":"J. Org. Chem."},{"issue":"12","key":"2026081709204643700_cit35","doi-asserted-by":"publisher","first-page":"1550","DOI":"10.1039\/B409604E","article-title":"Palladium nanoparticles obtained from palladium salts\nand tributylamine in molten tetrabutylammonium bromide: their use\nfor hydrogenolysis-free hydrogenation of olefins","volume":"28","author":"Le\nBras","year":"2004","journal-title":"New J. Chem."},{"issue":"3","key":"2026081709204643700_cit36","doi-asserted-by":"publisher","first-page":"429","DOI":"10.1007\/s11051-007-9270-2","article-title":"Potential\napplication of palladium nanoparticles as selective recyclable hydrogenation\ncatalysts","volume":"10","author":"Mukherjee","year":"2008","journal-title":"J. Nanopart. Res."},{"issue":"10","key":"2026081709204643700_cit37","doi-asserted-by":"publisher","first-page":"1404","DOI":"10.1002\/adsc.200404313","article-title":"Selective\nHydrogenation of 1,3-Butadiene to 1-Butene by Pd(0) Nanoparticles\nEmbedded in Imidazolium Ionic Liquids","volume":"347","author":"Umpierre","year":"2005","journal-title":"Adv.\nSynth. 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Med.\nChem."},{"key":"2026081709204643700_cit42","doi-asserted-by":"publisher","first-page":"1","DOI":"10.1016\/j.steroids.2016.07.009","article-title":"Synthesis and evaluation of new steroidal lactam conjugates with\naniline mustards as potential antileukemic therapeutics","volume":"115","author":"Trafalis","year":"2016","journal-title":"Steroids"},{"issue":"41","key":"2026081709204643700_cit43","doi-asserted-by":"publisher","first-page":"7367","DOI":"10.1016\/j.tetlet.2006.08.007","article-title":"Facile synthesis\nof ionic liquids\npossessing chiral carboxylates","volume":"47","author":"Allen","year":"2006","journal-title":"Tetrahedron\nLett."},{"issue":"7","key":"2026081709204643700_cit44","doi-asserted-by":"publisher","first-page":"935","DOI":"10.1039\/b821513h","article-title":"Chiral ionic\nliquids improved the asymmetric cycloaddition of CO2 to epoxides","volume":"11","author":"Zhang","year":"2009","journal-title":"Green Chem."},{"key":"2026081709204643700_cit45","doi-asserted-by":"publisher","first-page":"1529","DOI":"10.1135\/cccc20011529","article-title":"Simple NMR Determination\nof 5\u03b1\/5\u03b2 Configuration of 3-Oxosteroids","volume":"66","author":"Chodounska\u0301","year":"2001","journal-title":"Collect. Czech. Chem. Commun."},{"issue":"8","key":"2026081709204643700_cit46","doi-asserted-by":"publisher","first-page":"1825","DOI":"10.1039\/p19910001825","article-title":"Synthesis of samanine","author":"Cristofoli","year":"1991","journal-title":"J. Chem. Soc., Perkin\nTrans. 1"},{"issue":"7","key":"2026081709204643700_cit47","doi-asserted-by":"publisher","first-page":"1125","DOI":"10.1135\/cccc19991125","article-title":"Autoxidation vs hydrolysis in 16\nalpha-acyloxy steroids","volume":"64","author":"Slavikova","year":"1999","journal-title":"Collect. Czech. Chem.\nCommun."}],"container-title":["ACS Omega"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/acsomega.3c08963","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/acsodf\/article-pdf\/9\/6\/7043\/4435109\/ao3c08963.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/acsodf\/article-pdf\/9\/6\/7043\/4435109\/ao3c08963.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,8,17]],"date-time":"2026-08-17T13:32:48Z","timestamp":1786973568000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/acsodf\/article\/9\/6\/7043\/432611\/Stereoselective-Reduction-of-Steroidal-4-Ene-3"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2024,2,4]]},"references-count":47,"journal-issue":{"issue":"6","published-online":{"date-parts":[[2024,2,4]]},"published-print":{"date-parts":[[2024,2,13]]}},"URL":"https:\/\/doi.org\/10.1021\/acsomega.3c08963","relation":{},"ISSN":["2470-1343"],"issn-type":[{"value":"2470-1343","type":"electronic"}],"subject":[],"published":{"date-parts":[[2024,2,4]]}}}