{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,30]],"date-time":"2026-09-30T16:21:05Z","timestamp":1790785265090,"version":"4.1.0"},"reference-count":41,"publisher":"Wiley","issue":"3","license":[{"start":{"date-parts":[[2023,11,6]],"date-time":"2023-11-06T00:00:00Z","timestamp":1699228800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by-nc-nd\/4.0\/"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["ChemPlusChem"],"published-print":{"date-parts":[[2024,3]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>In this work, the initial steps of the mechanism of the Formose reaction (FR) is computationally studied using DFT methods. The FR has been considered to be a relevant process in the prebiotic evolution leading to several types of sugars or carbohydrates. These molecules are some of the basic building blocks of the life. The dimerization of formaldehyde was found to take place <jats:italic>via<\/jats:italic> an intramolecular deprotonation reaction, leading to the formation of an intermediate which, after an isomerization, forms a Ca\u2010complex of the <jats:italic>cis<\/jats:italic>\u2010enediol tautomer of glycolaldehyde. The aldol reaction of this complex with additional formaldehyde gave glyceraldehyde, the simplest aldotriose. The catalyst Ca(OH)<jats:sub>2<\/jats:sub> plays a dual role in the reaction, acting as a base (in the intramolecular deprotonation) and as Lewis acid (activating the carbonyl group) in the aldol addition.<\/jats:p>","DOI":"10.1002\/cplu.202300388","type":"journal-article","created":{"date-parts":[[2023,11,6]],"date-time":"2023-11-06T21:14:09Z","timestamp":1699305249000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":15,"title":["Prebiotic Synthesis of Glycolaldehyde and Glyceraldehyde from Formaldehyde: A Computational Study on the Initial Steps of the Formose Reaction"],"prefix":"10.1002","volume":"89","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-9496-3910","authenticated-orcid":false,"given":"Alessandro","family":"Venturini","sequence":"first","affiliation":[{"name":"Institute of Organic Synthesis and Photoreactivity (ISOF) National Research Council of Italy  Via P. Gobetti 101 40129 -Bologna Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2514-097X","authenticated-orcid":false,"given":"Javier","family":"Gonz\u00e1lez","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica Org\u00e1nica e Inorg\u00e1nica Universidad de Oviedo  c\/ Juli\u00e1n Claver\u00eda 8 33006- Oviedo Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2023,11,6]]},"reference":[{"key":"e_1_2_9_1_1","doi-asserted-by":"publisher","DOI":"10.1101\/cshperspect.a002089"},{"key":"e_1_2_9_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.0c00409"},{"key":"e_1_2_9_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr2004844"},{"key":"e_1_2_9_4_1","unstructured":"TheHadean Eon(International Commision on Stratigraphy www.stratigraphy.org) is the period betwen \u22124600 and \u22124000 millions of years."},{"key":"e_1_2_9_5_1","unstructured":"The molecules essential for life seems to have originated in a very early period of the history of the Earth (usually calledPrebiotic Evolution). Even though that the hypothesis and proposals about this process have changed it seems appropriate to mention the pioneer experiments by Miller:"},{"key":"e_1_2_9_6_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.117.3046.528"},{"key":"e_1_2_9_7_2","doi-asserted-by":"publisher","DOI":"10.1007\/s11084-015-9468-8"},{"key":"e_1_2_9_8_2","first-page":"381","volume":"47","author":"Scherer S.","year":"2017","journal-title":"Ibid."},{"key":"e_1_2_9_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.3c00908"},{"key":"e_1_2_9_10_1","unstructured":"See for example:"},{"key":"e_1_2_9_11_2","volume-title":"The Organic Chemistry of Biological Pathways","author":"McMurry J.","year":"2005"},{"key":"e_1_2_9_12_2","doi-asserted-by":"publisher","DOI":"10.1002\/9780470742761"},{"key":"e_1_2_9_13_1","unstructured":"The name\u201cFormose\u201dderives from the contraction of the words formaldehyde and aldose."},{"key":"e_1_2_9_14_1","unstructured":"\u00a0"},{"key":"e_1_2_9_15_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1092464"},{"key":"e_1_2_9_16_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja201769f"},{"key":"e_1_2_9_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja410886c"},{"key":"e_1_2_9_18_1","unstructured":"\u00a0"},{"key":"e_1_2_9_19_2","doi-asserted-by":"publisher","DOI":"10.1002\/cssc.201400040"},{"key":"e_1_2_9_20_2","doi-asserted-by":"publisher","DOI":"10.3390\/life10080125"},{"key":"e_1_2_9_21_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.precamres.2008.04.002"},{"key":"e_1_2_9_22_1","unstructured":"\u00a0"},{"key":"e_1_2_9_23_2","doi-asserted-by":"publisher","DOI":"10.1002\/tcr.201600022"},{"key":"e_1_2_9_24_2","doi-asserted-by":"publisher","DOI":"10.1038\/216453a0"},{"key":"e_1_2_9_25_1","unstructured":"Likely the most important side reaction to occur in these conditions is the Cannizzaro reaction (a disproportionation of non-enolizable aldehydes in a strongly basic medium) of formaldehyde leading to methanol and formate."},{"key":"e_1_2_9_26_1","doi-asserted-by":"publisher","DOI":"10.1089\/ast.2017.1800"},{"key":"e_1_2_9_27_1","first-page":"1280","volume-title":"March\u2018s Advanced Organic Chemistry: Reactions, Mechanisms, and Structure","author":"Smith M. 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B.","year":"2007"},{"key":"e_1_2_9_38_1","unstructured":"Calcium hydroxide is the base employed in the experiments carried out by van Duppen et\u2005al. (ref. 6) and Appayee and Breslow (ref. 9c)."},{"key":"e_1_2_9_39_1","doi-asserted-by":"publisher","DOI":"10.1039\/b508541a"},{"key":"e_1_2_9_39_2","doi-asserted-by":"publisher","DOI":"10.1039\/b515623h"},{"key":"e_1_2_9_40_1","unstructured":"Gaussian 16 Revision B.01 M.\u2005J. Frisch G.\u2005W. Trucks H.\u2005B. Schlegel G.\u2005E. Scuseria M.\u2005A. Robb J.\u2005R. Cheeseman G. Scalmani V. Barone G.\u2005A. Petersson H. Nakatsuji X. Li M. Caricato A.\u2005V. Marenich J. Bloino B.\u2005G. Janesko R. Gomperts B. Mennucci H.\u2005P. Hratchian J.\u2005V. Ortiz A.\u2005F. Izmaylov J.\u2005L. Sonnenberg D. Williams-Young F. Ding F. Lipparini F. Egidi J. Goings B. Peng A. Petrone T. Henderson D. Ranasinghe V.\u2005G. Zakrzewski J. Gao N. Rega G. Zheng W. Liang M. Hada M. Ehara K. Toyota R. Fukuda J. Hasegawa M. Ishida T. Nakajima Y. Honda O. Kitao H. Nakai T. Vreven K. Throssell J.\u2005A. Montgomery\u2005Jr. J.\u2005E. Peralta F. Ogliaro M.\u2005J. Bearpark J.\u2005J. Heyd E.\u2005N. Brothers K.\u2005N. Kudin V.\u2005N. Staroverov T.\u2005A. Keith R. Kobayashi J. Normand K. Raghavachari A.\u2005P. Rendell J.\u2005C. Burant S.\u2005S. Iyengar J. Tomasi M. Cossi J.\u2005M. Millam M. Klene C. Adamo R. Cammi J.\u2005W. Ochterski R.\u2005L. Martin K. Morokuma O. Farkas J.\u2005B. Foresman D.\u2005J. Fox Gaussian Inc. Wallingford CT 2016."}],"container-title":["ChemPlusChem"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/cplu.202300388","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,13]],"date-time":"2025-10-13T15:52:51Z","timestamp":1760370771000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/cplu.202300388"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,11,6]]},"references-count":41,"journal-issue":{"issue":"3","published-print":{"date-parts":[[2024,3]]}},"alternative-id":["10.1002\/cplu.202300388"],"URL":"https:\/\/doi.org\/10.1002\/cplu.202300388","archive":["Portico"],"relation":{},"ISSN":["2192-6506","2192-6506"],"issn-type":[{"value":"2192-6506","type":"print"},{"value":"2192-6506","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,11,6]]},"assertion":[{"value":"2023-07-25","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2023-11-06","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202300388"}}