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In parallel, considerable progress has been made in elucidating the reaction mechanisms. In this account, we discuss the fundamental features of ThDP\u2010dependent enzyme catalysis, focusing on developments reported since the beginning of this century, with an emphasis on studies from recent years. We provide an overview of advances in C\u2500C forming reactions, the relationships of sequence, structure, and function, as well as enzyme classifications and biocatalytic applications that have broadened ThDP\u2010dependent research. In addition, we highlight newly described activities, including C\n                    <jats:sub>1<\/jats:sub>\n                    elongation and photobiocatalytic transformations, that have recently expanded the known catalytic scope of ThDP\u2010dependent enzymes and paved the way to previously unexpected directions. Focusing on non\u2010canonical enzymes and less established properties of ThDP\u2010dependent enzymes, we also outline some of the remaining open questions and, at the same time, exciting new avenues for future research. The review aims to offer concise and critical insights into the current state of knowledge regarding ThDP\u2010dependent enzymes. By selecting recent key developments and remaining challenges, we hope to stimulate further discoveries through an open\u2010minded approach.\n                  <\/jats:p>","DOI":"10.1002\/chem.71699","type":"journal-article","created":{"date-parts":[[2026,9,24]],"date-time":"2026-09-24T03:12:22Z","timestamp":1790219542000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Thiamine Diphosphate\u2010Dependent Biocatalysis in the 21\n                    <sup>st<\/sup>\n                    Century"],"prefix":"10.1002","author":[{"ORCID":"https:\/\/orcid.org\/0009-0000-9294-2932","authenticated-orcid":false,"given":"Lucrezia","family":"Lanza","sequence":"first","affiliation":[{"name":"Institute of Pharmaceutical Sciences University of Freiburg  Freiburg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0006-7518-1880","authenticated-orcid":false,"given":"Daniela","family":"Bjarnesen","sequence":"additional","affiliation":[{"name":"Institute of Pharmaceutical Sciences University of Freiburg  Freiburg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2742-4992","authenticated-orcid":false,"given":"Michael","family":"M\u00fcller","sequence":"additional","affiliation":[{"name":"Institute of Pharmaceutical Sciences University of Freiburg  Freiburg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,9,23]]},"reference":[{"issue":"115","key":"e_1_2_8_2_1","first-page":"282","article-title":"\u00dcber ein kohlenstoffketten kn\u00fcpfendes ferment (carboligase)","author":"Neuberg C.","year":"1921","journal-title":"Biochemische Zeitschrift"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0922\u2010338X(97)81900\u20109"},{"issue":"294","key":"e_1_2_8_4_1","first-page":"188","article-title":"On Cocarboxylase","author":"Lohmann K.","year":"1937","journal-title":"Biochemische Zeitschrift"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja01564a064"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja01547a064"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1016\/0006\u20103002(61)90747\u20108"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1016\/0014\u20105793(89)81064\u20106"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0167\u20104838(98)00067\u20103"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja01100a526"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja01100a525"},{"key":"e_1_2_8_12_1","volume-title":"Methods in Enzymology","author":"Hegeman G. 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