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Chiral tertiary \u03b1\u2010hydroxy ketones are formed in this process. The ThDP\u2010dependent enzymes that catalyze C\u2010branching reactions belong to one of three enzymatic superfamilies: decarboxylases, transketolases, and \u03b1\u2010ketoacid dehydrogenases 2, but branching of keto sugars has only been demonstrated for decarboxylases. In this study, we showed that an \u03b1\u2010ketoacid dehydrogenase is responsible for C\u2010branching of the deoxyketo sugar amycolose in the biosynthesis of kibdelomycin in <jats:italic>Kibdelosporangium sp<\/jats:italic>. MA7385. In addition, we characterized an amino transferase in the same biosynthetic gene cluster (BGC) that accepts a sterically demanding tertiary \u03b1\u2010hydroxy ketone in a downstream reaction. Subsequently, we identified approximately 400 similar BGCs in silico, suggesting that there is a large diversity of possible ThDP\u2010dependent enzymes catalyzing the C\u2010branching of keto sugars and subsequent modifications.<\/jats:p>","DOI":"10.1002\/anie.202403535","type":"journal-article","created":{"date-parts":[[2024,7,2]],"date-time":"2024-07-02T02:08:46Z","timestamp":1719886126000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["Identification of Kibdelomycin and Related Biosynthetic Gene Clusters and Characterization of the C\u2010Branching of Amycolose"],"prefix":"10.1002","author":[{"ORCID":"https:\/\/orcid.org\/0009-0002-7166-1490","authenticated-orcid":false,"given":"Leonhard","family":"Krug","sequence":"first","affiliation":[{"name":"Institut f\u00fcr Pharmazeutische Wissenschaften Albert-Ludwigs-Universit\u00e4t Freiburg  Albertstrasse 25 79104 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":"Institut f\u00fcr Pharmazeutische Wissenschaften Albert-Ludwigs-Universit\u00e4t Freiburg  Albertstrasse 25 79104 Freiburg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0000-9294-2932","authenticated-orcid":false,"given":"Lucrezia","family":"Lanza","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Pharmazeutische Wissenschaften Albert-Ludwigs-Universit\u00e4t Freiburg  Albertstrasse 25 79104 Freiburg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0002-1750-5809","authenticated-orcid":false,"given":"Lucia","family":"Lindemann","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Pharmazeutische Wissenschaften Albert-Ludwigs-Universit\u00e4t Freiburg  Albertstrasse 25 79104 Freiburg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8247-1356","authenticated-orcid":false,"given":"Nico D.","family":"Fessner","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Pharmazeutische Wissenschaften Albert-Ludwigs-Universit\u00e4t Freiburg  Albertstrasse 25 79104 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":"Institut f\u00fcr Pharmazeutische Wissenschaften Albert-Ludwigs-Universit\u00e4t Freiburg  Albertstrasse 25 79104 Freiburg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2024,9,12]]},"reference":[{"key":"e_1_2_3_1_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chembiol.2011.06.011"},{"key":"e_1_2_3_2_1","unstructured":"\u00a0"},{"key":"e_1_2_3_3_2","doi-asserted-by":"publisher","DOI":"10.1128\/AAC.00382-15"},{"key":"e_1_2_3_4_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.btre.2022.e00728"},{"key":"e_1_2_3_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/cb5001197"},{"key":"e_1_2_3_6_1","doi-asserted-by":"publisher","DOI":"10.1038\/ja.2010.1"},{"key":"e_1_2_3_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.1c11477"},{"key":"e_1_2_3_8_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.bmcl.2012.09.071"},{"key":"e_1_2_3_9_1","unstructured":"\u00a0"},{"key":"e_1_2_3_10_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.copbio.2005.10.002"},{"key":"e_1_2_3_11_2","doi-asserted-by":"publisher","DOI":"10.1038\/nature05814"},{"key":"e_1_2_3_12_1","unstructured":"\u00a0"},{"key":"e_1_2_3_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.9b00650"},{"key":"e_1_2_3_14_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.202200761"},{"key":"e_1_2_3_15_1","unstructured":"\u00a0"},{"key":"e_1_2_3_16_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202206183"},{"key":"e_1_2_3_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.2c00647"},{"key":"e_1_2_3_18_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200801204"},{"key":"e_1_2_3_19_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202113405"},{"key":"e_1_2_3_20_1","unstructured":"P. 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