{"doi":"10.1021/acs.macromol.5c01040","title":"Synthesis, Characterization, and Polymerization of 4′-Acyl(oxy) Alkenyl Azlactone Monomers Designed Using a Steglich Rearrangement Approach","abstract":"Monomers and polymers containing amine-reactive azlactone functionality are useful for the design of a broad range of soft materials. The vinyl monomer 2-vinyl-4,4-dimethylazlactone (VDMA), which can be readily polymerized to poly(2-vinyl-4,4-dimethylazlactone) (PVDMA) using free radical methods, has been widely used for these purposes, but the synthesis of other alkenyl azlactone derivatives having other substituents in the 4-position presents several challenges. Here, we report the synthesis and characterization of novel 4′-acyl(oxy) alkenyl azlactones using approaches based on the Steglich rearrangement. We report both stepwise and one-pot Steglich rearrangement approaches to the synthesis of 2-isopropenyl-4-methyl-4′-acylazlactones from 2-isopropenyl-4-methylazlactone and acyl halides using DMAP and DMAP derivatives as nucleophilic acyl transfer catalysts. This approach enables the synthesis of disubstituted alkenyl azlactone derivatives having a variety of substituted alkyl and aryl ester and ketone groups in the 4-position. The resulting alkenyl azlactones react readily through ring-opening reactions with amine-based nucleophiles and can also be polymerized by AIBN-initiated free radical polymerization to yield new amine-reactive polymers. In addition, we demonstrate an approach to the synthesis of enantioenriched alkenyl azlactone monomers using an asymmetric DMAP derivative and a novel procedure for the in situ activation of carboxylic acids that eliminates the need for acyl halide-based starting materials during the Steglich rearrangement. Our results provide new and useful approaches to the design of alkenyl azlactone-based monomers and polymers with novel structures that would be difficult to synthesize using conventional methods.","journal":"Macromolecules","year":2025,"id":569259,"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":0,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9536,"is_data_producer":false,"deposit_databanks":null,"is_oa":true,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":"2025-01-01","fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":732677,"name":"David M. Lynn","orcid":"0000-0002-3140-8637","position":1,"is_corresponding":false},{"id":1474194,"name":"William M. Breining","orcid":"0000-0001-6022-766X","position":0,"is_corresponding":true}],"reference_count":62,"raw_metadata":null,"created_at":"2026-07-19T02:56:59.652443Z","pmid":"41767476","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":[]}