{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,16]],"date-time":"2026-10-16T15:45:59Z","timestamp":1792165559638,"version":"4.4.0"},"reference-count":45,"publisher":"Wiley","issue":"51","license":[{"start":{"date-parts":[[2024,10,31]],"date-time":"2024-10-31T00:00:00Z","timestamp":1730332800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"},{"start":{"date-parts":[[2024,10,31]],"date-time":"2024-10-31T00:00:00Z","timestamp":1730332800000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2024,12,16]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>\n                    A bifunctional thiourea\u2010amine\u2010based organocatalyst (Takemoto's catalyst), employing a metal\u2010free approach, is presented for the regioselective ring\u2010opening polymerization (ROP) of optically active (\n                    <jats:italic>D<\/jats:italic>\n                    and\n                    <jats:italic>L<\/jats:italic>\n                    ) methyl glycolide (MG). In this study, a chiral version of Takemoto's catalyst efficiently promotes the ROP of MG at room temperature, yielding poly(lactic\u2010\n                    <jats:italic>co<\/jats:italic>\n                    \u2010glycolic acids) (PLGAs) with predicted molecular weights and narrow polydispersity indices (PDI\u22641.2). These PLGAs exhibit highly alternating structures without transesterification, as confirmed by\n                    <jats:sup>1<\/jats:sup>\n                    H NMR, SEC, and MALDI\u2010TOF analyses. Additionally, various macromolecular architectures, including linear and star\u2010shaped PLGAs, were successfully synthesized using the corresponding multi\u2010functional alcohol initiators while maintaining the same alternating structures and regioselectivity with PLGA obtained from benzyl alcohol as initiator. Computational studies were conducted to elucidate the mechanism of alternating PLGA formation, revealing two key transition states (TSs): TS\u20101, which implicates the nucleophilic attack of the hydroxyl group of the initiator or propagating chain on the carbonyl carbon of MG, and TS\u20102, which involves the subsequent ring\u2010opening of the cyclic ester. The results indicate that ring\u2010opening occurs at both the glycolyl and lactyl sites, with a preference for the glycolyl site, as supported by experimental results. The resulting atactic PLGAs are amorphous, rendering them suitable for drug delivery applications.\n                  <\/jats:p>","DOI":"10.1002\/anie.202411809","type":"journal-article","created":{"date-parts":[[2024,9,11]],"date-time":"2024-09-11T11:35:02Z","timestamp":1726054502000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":18,"title":["Controlled Ring\u2010Opening Polymerization of Methyl Glycolide with Bifunctional Organocatalyst"],"prefix":"10.1002","volume":"63","author":[{"given":"Prakash","family":"Alagi","sequence":"first","affiliation":[{"name":"Polymer Synthesis Laboratory Chemistry Program KAUST Catalysis Center Physical Sciences and Engineering Division King Abdullah University of Science and Technology (KAUST)  Thuwal 23955 Saudi Arabia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shrikant B.","family":"Nikam","sequence":"additional","affiliation":[{"name":"Polymer Synthesis Laboratory 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