{"doi":"10.1021/jacs.2c13047","title":"Breaking the <i>tert</i> -Butyllithium Contact Ion Pair: A Gateway to Alternate Selectivity in Lithiation Reactions","abstract":"The effects of Lewis basic phosphoramides on the aggregate structure of t- BuLi have been investigated in detail by NMR and DFT methods. It was determined that hexamethylphosphoramide (HMPA) can shift the equilibrium of t- BuLi to include the triple ion pair ( t -Bu–Li– t -Bu) − /HMPA 4 Li + which serves as a reservoir for the highly reactive separated ion pair t -Bu – /HMPA 4 Li + . Because the Li-atom’s valences are saturated in this ion pair, the Lewis acidity is significantly decreased; in turn, the basicity is maximized which allowed for the typical directing effects within oxygen heterocycles to be overridden and for remote sp 3 C–H bonds to be deprotonated. Furthermore, these newly accessed lithium aggregation states were leveraged to develop a simple γ-lithiation and capture protocol of chromane heterocycles with a variety of alkyl halide electrophiles in good yields.","journal":"Journal of the American Chemical Society","year":2023,"id":334559,"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":21,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9647,"is_data_producer":false,"deposit_databanks":null,"is_oa":true,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":"2023-01-01","fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":1063012,"name":"Jeanette Piña","orcid":"0000-0003-3970-9263","position":1,"is_corresponding":false},{"id":961467,"name":"Achyut Ranjan Gogoi","orcid":"0000-0002-7609-3720","position":2,"is_corresponding":false},{"id":703976,"name":"Rémy F. Lalisse","orcid":"0000-0002-4556-5641","position":3,"is_corresponding":false},{"id":386019,"name":"Andrew Nguyen","orcid":"0000-0003-3796-1625","position":4,"is_corresponding":false},{"id":348357,"name":"Osvaldo Gutiérrez","orcid":"0000-0001-8151-7519","position":5,"is_corresponding":false},{"id":1063013,"name":"Andy A. Thomas","orcid":"0000-0001-6336-5566","position":6,"is_corresponding":false},{"id":1063011,"name":"Michael P. Crockett","orcid":"0000-0002-6165-2841","position":0,"is_corresponding":true}],"reference_count":88,"raw_metadata":null,"created_at":"2026-07-19T01:09:48.843291Z","pmid":"37133911","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":[]}