{"doi":"10.1073/pnas.2106202118","title":"The LarB carboxylase/hydrolase forms a transient cysteinyl-pyridine intermediate during nickel-pincer nucleotide cofactor biosynthesis","abstract":"Significance Carboxylation of nonactivated carbon atoms in aromatic rings is of considerable synthetic importance, but these reactions typically require harsh conditions or highly reactive reagents. In this study, the mechanism of pyridinium ring carboxylation is established for LarB, an enzyme that is essential for biosynthesis of the recently discovered nickel-pincer nucleotide cofactor found in a diverse family of racemases or epimerases. Structural and mutagenesis methods were used to define a new paradigm for carboxylation of a pyridinium ring in which a cysteinyl-pyridine ring intermediate enhances the nucleophilicity of the adjacent carbon atom for reaction with carbon dioxide.","journal":"Proceedings of the National Academy of Sciences","year":2021,"id":187049,"datarank":0.0,"base_score":0.0,"endowment":0.0,"self_citation_contribution":0.0,"citation_network_contribution":0.0,"self_endowment_contribution":0.0,"citer_contribution":0.0,"corpus_percentile":null,"corpus_rank":null,"citation_count":19,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9595,"is_data_producer":false,"deposit_databanks":null,"is_oa":true,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":"2021-01-01","fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":745989,"name":"Shramana Chatterjee","orcid":"0000-0001-8765-1102","position":1,"is_corresponding":false},{"id":745990,"name":"Zia Tariq","orcid":"0000-0001-5795-4356","position":2,"is_corresponding":false},{"id":745991,"name":"Satyanarayana Lagishetty","orcid":"0000-0002-5329-1257","position":3,"is_corresponding":false},{"id":489879,"name":"Benoît Desguin","orcid":"0000-0002-5004-6918","position":4,"is_corresponding":false},{"id":334698,"name":"Jian Hu","orcid":"0000-0001-6657-9826","position":5,"is_corresponding":false},{"id":475596,"name":"Robert P. Hausinger","orcid":"0000-0002-3643-2054","position":6,"is_corresponding":false},{"id":745988,"name":"Joel A. Rankin","orcid":"0000-0002-9775-4508","position":0,"is_corresponding":true}],"reference_count":19,"raw_metadata":null,"created_at":"2026-07-18T23:48:51.315888Z","pmid":"34548397","pmcid":null,"fwci":null,"citation_percentile":null,"influential_citations":0,"oa_status":null,"license":null,"views":0,"total_file_size_bytes":0,"version_count":0,"fair_f":null,"fair_a":null,"fair_i":null,"fair_r":null,"fair_zscore":null,"fair_rationale":null,"fair_model":null,"fair_agent_version":null,"fair_fulltext_source":null,"fair_has_llm":null,"fair_computed_at":null,"clinical_trials":[],"software_tools":[],"db_accessions":[],"linked_datasets":[],"topics":[]}