{"doi":"10.1002/ejoc.202000976","title":"Mechanistic Investigations of the Pd‐Catalyzed Hydrogenolysis of Ketene Heterodimer β‐Lactones","abstract":"Catalytic hydrogenolysis of the Z ‐isomer of a series of aryl‐substituted ketene heterodimer β‐lactones facilitated access to deoxypropionate derivatives with a dr ranging from 54:46 to 86:14, favoring the anti ‐isomer, and with excellent transfer of chirality (91 → 99 % ee for 13 examples). Although X = 4‐F was determined to provide optimal diastereoselectivity ( dr 86:14), a non‐linear relationship between diastereoselectivity and aryl substituent σ values was found. For cases where a para ‐ or ortho ‐EWG was present on the aryl ring of the ketene heterodimer, formation of significant amounts of β‐lactone (20–44 %) as by‐product was observed. The results of a number of control reactions point to anti ‐β‐elimination and an anti ‐selective hydrogenation of an E ‐isomer olefin intermediate being key steps in the reaction mechanism. The synthetic potential of the deoxypropionate derivative products was demonstrated by oxidative conversion into a 1,5‐difunctionalized deoxypropionate motif.","journal":"European Journal of Organic Chemistry","year":2020,"id":85245,"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":7,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.952,"is_data_producer":false,"deposit_databanks":null,"is_oa":false,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":"2020-01-01","fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":437017,"name":"Mukulesh Mondal","orcid":null,"position":1,"is_corresponding":false},{"id":436160,"name":"Shi Chen","orcid":"0000-0002-6889-187X","position":2,"is_corresponding":false},{"id":437018,"name":"Ahmad Ibrahim","orcid":null,"position":3,"is_corresponding":false},{"id":431275,"name":"Dylan J. Twardy","orcid":null,"position":4,"is_corresponding":false},{"id":436161,"name":"Nessan J. Kerrigan","orcid":"0000-0003-3643-5260","position":5,"is_corresponding":false},{"id":436159,"name":"Manashi Panda","orcid":"0009-0007-6772-167X","position":0,"is_corresponding":true}],"reference_count":69,"raw_metadata":null,"created_at":"2026-07-18T21:56:02.794896Z","pmid":null,"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":[]}