{"doi":"10.1002/anie.202003029","title":"Predicting Absolute Rate Constants for Huisgen Reactions of Unsaturated Iminium Ions with Diazoalkanes","abstract":"<jats:title>Abstract</jats:title><jats:p>The kinetics and stereochemistry of the reactions of iminium ions derived from cinnamaldehydes and MacMillan's imidazolidinones with diphenyldiazomethane and aryldiazomethanes were investigated experimentally and with DFT calculations. The reactions of diphenyldiazomethane with iminium ions derived from MacMillan's second‐generation catalysts gave 3‐aryl‐2,2‐diphenylcyclopropanecarbaldehydes with yields &gt;90 % and enantiomeric ratios of ≥90:10. Predominantly 2:1 products were obtained from the corresponding reactions with monoaryldiazomethanes. The measured rate constants are in good agreement with the rate constants derived from the one‐center nucleophilicity parameters <jats:italic>N</jats:italic> and <jats:italic>s</jats:italic><jats:sub>N</jats:sub> of diazomethanes and the one‐center electrophilicity parameters <jats:italic>E</jats:italic> of iminium ions as well as with quantum chemically calculated activation energies.</jats:p>","journal":"Angewandte Chemie International Edition","year":2020,"id":588718,"datarank":0.7431620821231295,"base_score":2.995732273553991,"endowment":2.995732273553991,"self_citation_contribution":0.4493598410330987,"citation_network_contribution":0.2938022410900308,"self_endowment_contribution":0.4493598410330987,"citer_contribution":0.2938022410900308,"corpus_percentile":null,"corpus_rank":null,"citation_count":19,"citer_count":13,"citers_with_citation_signal":11,"citers_with_endowment":11,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":null,"is_data_producer":false,"deposit_databanks":null,"is_oa":false,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":null,"fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":355411,"name":"Quan Chen","orcid":"0000-0003-4436-3471","position":1,"is_corresponding":false},{"id":56632,"name":"Robert J. 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The reactions of diphenyldiazomethane with iminium ions derived from MacMillan's second‐generation catalysts gave 3‐aryl‐2,2‐diphenylcyclopropanecarbaldehydes with yields &gt;90 % and enantiomeric ratios of ≥90:10. Predominantly 2:1 products were obtained from the corresponding reactions with monoaryldiazomethanes. The measured rate constants are in good agreement with the rate constants derived from the one‐center nucleophilicity parameters <jats:italic>N</jats:italic> and <jats:italic>s</jats:italic><jats:sub>N</jats:sub> of diazomethanes and the one‐center electrophilicity parameters <jats:italic>E</jats:italic> of iminium ions as well as with quantum chemically calculated activation energies.</jats:p>","is_dataset_classified":null,"base_score":2.995732273553991,"endowment":2.995732273553991,"datacite_reuse_total":0,"file_count":0,"downloads":0,"views":0,"has_version_chain":false,"is_dataset":false,"is_oa":false,"pmid":"32259362","pmcid":"PMC7383640","openalex_id":"https://openalex.org/W3014655192","authors":[],"funders":[{"funder_name":"National Natural Science Foundation of China","grant_id":"21672124, 21602116, 21772098, 91745101","title":null},{"funder_name":"Tsinghua University","grant_id":"20131080083, 20141081295","title":null},{"funder_name":"Verband der Chemischen Industrie","grant_id":"","title":null},{"funder_name":"Verband der Chemischen Industrie","grant_id":"","title":null}],"total_grants":4,"fwci":1.5253,"citation_percentile":0.80673807,"influential_citations":0,"citation_trend":[{"year":2020,"count":6},{"year":2021,"count":3},{"year":2022,"count":4},{"year":2023,"count":3},{"year":2024,"count":1},{"year":2025,"count":2}],"oa_status":"hybrid","license":"cc-by","oa_locations":[{"url":"https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/anie.202003029","host_type":"journal"},{"url":"https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/anie.202003029","host_type":"publisher"},{"url":"https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fanie.202003029","host_type":"publisher"},{"url":"https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.202003029","host_type":"publisher"},{"url":"https://onlinelibrary.wiley.com/doi/full-xml/10.1002/anie.202003029","host_type":"publisher"},{"url":"https://doi.org/10.1002/anie.202003029","host_type":"journal"},{"url":"https://pubmed.ncbi.nlm.nih.gov/32259362","host_type":"repository"},{"url":"http://nbn-resolving.de/urn:nbn:de:bvb:19-epub-89882-2","host_type":"journal"},{"url":"https://www.ncbi.nlm.nih.gov/pmc/articles/7383640","host_type":"repository"},{"url":"https://europepmc.org/articles/PMC7383640","host_type":"Europe_PMC"},{"url":"https://europepmc.org/articles/PMC7383640?pdf=render","host_type":"Europe_PMC"}],"fields_of_study":["Cyclopropane Reaction Mechanisms","Oxidative Organic Chemistry Reactions","Asymmetric Synthesis and Catalysis"],"mesh_terms":[],"keywords":["Iminium","Chemistry","Electrophile","Nucleophile","Reaction rate constant","Ion","Thermochemistry","Enantiomer","Computational chemistry","Catalysis","Kinetics","Physical chemistry","Organic chemistry","Physics","Organocatalysis","Electrophiles","Nucleophiles","Diazoalkanes"],"sdg_mappings":[{"sdg_number":0,"sdg_label":"Clean water and sanitation"}],"linked_datasets":[],"clinical_trials":[],"software_tools":[],"database_accessions":[],"source":"live","citation_network_status":"fetched"},"created_at":"2026-07-22T19:38:55.769806Z","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":[]}