{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Yang X"],"funding":["Division of Chemistry","Army Research Office","National Institute of General Medical Sciences","NIGMS NIH HHS","Army Research Laboratory"],"pagination":["935-942"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC8955669"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["12(2)"],"pubmed_abstract":["Vitamin B<sub>12</sub> derivatives catalyze a wide range of organic transformations, but B<sub>12</sub>-dependent enzymes are underutilized in biocatalysis relative to other metalloenzymes. In this study, we engineered a variant of the transcription factor CarH, called CarH*, that catalyzes styrene C-H alkylation with improved yields (2-6.5-fold) and selectivity relative to cobalamin. While the native function of CarH involves transcription regulation via adenosylcobalamin (AdoCbl) Co(III)-carbon bond cleavage and <i>β</i>-hydride elimination to generate 4',5'-didehydroadenosine, CarH*-catalyzed styrene alkylation proceeds via non-native oxidative addition and olefin addition coupled with a native-like <i>β</i>-hydride elimination. Mechanistic studies on this reaction echo findings from ea"],"journal":["ACS catalysis"],"pubmed_title":["Controlling Non-Native Cobalamin Reactivity and Catalysis in the Transcription Factor CarH."],"pmcid":["PMC8955669"],"funding_grant_id":["R01 GM115665","W911NF-19-1-0074","CHE-1808133","T32 GM131994"],"pubmed_authors":["Yang X","Jiang Y","Zubi YS","Baker LA","Gerroll BHR","Lewis JC","Kumar A"],"additional_accession":[]},"is_claimable":false,"name":"Controlling Non-Native Cobalamin Reactivity and Catalysis in the Transcription Factor CarH.","description":"Vitamin B<sub>12</sub> derivatives catalyze a wide range of organic transformations, but B<sub>12</sub>-dependent enzymes are underutilized in biocatalysis relative to other metalloenzymes. In this study, we engineered a variant of the transcription factor CarH, called CarH*, that catalyzes styrene C-H alkylation with improved yields (2-6.5-fold) and selectivity relative to cobalamin. While the native function of CarH involves transcription regulation via adenosylcobalamin (AdoCbl) Co(III)-carbon bond cleavage and <i>β</i>-hydride elimination to generate 4',5'-didehydroadenosine, CarH*-catalyzed styrene alkylation proceeds via non-native oxidative addition and olefin addition coupled with a native-like <i>β</i>-hydride elimination. Mechanistic studies on this reaction echo findings from ea","dates":{"release":"2022-01-01T00:00:00Z","publication":"2022 Jan","modification":"2026-05-30T14:44:17.337Z","creation":"2024-11-09T22:30:01.276Z"},"accession":"S-EPMC8955669","cross_references":{"pubmed":["35340760"],"doi":["10.1021/acscatal.1c04748"]}}