{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,1]],"date-time":"2026-10-01T00:05:23Z","timestamp":1790813123235,"version":"4.1.0"},"reference-count":70,"publisher":"Wiley","license":[{"start":{"date-parts":[[2026,9,30]],"date-time":"2026-09-30T00:00:00Z","timestamp":1790726400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"},{"start":{"date-parts":[[2026,9,30]],"date-time":"2026-09-30T00:00:00Z","timestamp":1790726400000},"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"],"abstract":"<jats:title>ABSTRACT<\/jats:title>\n                  <jats:p>\n                    Thiazoles are ubiquitous motifs in bioactive molecules, making strategies for the stereospecific installation of chiral C(sp\n                    <jats:sup>3<\/jats:sup>\n                    )\u2010rich substituents on this scaffold particularly valuable for drug discovery. However, achieving such transformations remains nontrivial, as conventional C(sp\n                    <jats:sup>2<\/jats:sup>\n                    )\u2013C(sp\n                    <jats:sup>3<\/jats:sup>\n                    ) cross\u2010coupling approaches are often compromised by catalyst deactivation and deleterious side reactions, such as\n                    <jats:italic>\u03b2<\/jats:italic>\n                    \u2010hydride elimination. Although electrophile\u2010mediated coupling of alkyl boronic esters with lithiated aromatic compounds offers a potential route to C(sp\n                    <jats:sup>2<\/jats:sup>\n                    )\u2013C(sp\n                    <jats:sup>3<\/jats:sup>\n                    ) bond formation, it is ineffective for thiazoles because the heteroaromatic core lacks sufficient nucleophilicity to engage electrophiles and promote productive 1,2\u2010migration. Herein, we report a lithiation\u2013borylation\u2013aromatic Pummerer (LiBAP) strategy that enables stereospecific C5 cross\u2010coupling of thiazoles with boronic esters. A pendant sulfinyl group enables exocyclic electrophilic activation, triggering a Pummerer\u2010type 1,2\u2010migration while avoiding unproductive C\u2500B bond fragmentation. The reaction proceeds with complete stereospecificity and broad functional\u2010group tolerance, furnishing a C2 sulfide handle on thiazole that serves as a versatile linchpin for downstream C\u2013S diversification. A formal asymmetric synthesis of a bioactive thiazole\n                    <jats:italic>\u03b3<\/jats:italic>\n                    \u2010secretase inhibitor was demonstrated to further highlight the synthetic utility of our LiBAP protocol.\n                  <\/jats:p>","DOI":"10.1002\/anie.1701592","type":"journal-article","created":{"date-parts":[[2026,9,30]],"date-time":"2026-09-30T23:44:38Z","timestamp":1790811878000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Aromatic Pummerer\u2010Promoted Stereospecific Cross\u2010Coupling of Thiazoles With Boronic Esters"],"prefix":"10.1002","author":[{"given":"Mark John P.","family":"Mandigma","sequence":"first","affiliation":[{"name":"School of Chemistry University of Bristol  Bristol UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Julien","family":"Lefranc","sequence":"additional","affiliation":[{"name":"Merck KGaA  Darmstadt Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4771-3799","authenticated-orcid":false,"given":"Louise","family":"Eagling","sequence":"additional","affiliation":[{"name":"Merck KGaA  Darmstadt Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3155-1847","authenticated-orcid":false,"given":"Jasper L.","family":"Tyler","sequence":"additional","affiliation":[{"name":"School of Chemistry University of Bristol  Bristol UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0344-6430","authenticated-orcid":false,"given":"Varinder K.","family":"Aggarwal","sequence":"additional","affiliation":[{"name":"School of Chemistry University of Bristol  Bristol UK"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,9,30]]},"reference":[{"key":"e_1_2_6_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr0306790"},{"key":"e_1_2_6_3_1","doi-asserted-by":"publisher","DOI":"10.1016\/bs.aihch.2016.11.002"},{"key":"e_1_2_6_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jmedchem.2c00473"},{"key":"e_1_2_6_5_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0RA09198G"},{"key":"e_1_2_6_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/jm901241e"},{"key":"e_1_2_6_7_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.drudis.2013.07.011"},{"key":"e_1_2_6_8_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.drudis.2016.04.023"},{"key":"e_1_2_6_9_1","doi-asserted-by":"publisher","DOI":"10.3389\/fchem.2018.00460"},{"key":"e_1_2_6_10_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41570\u2010025\u201000688\u20105"},{"key":"e_1_2_6_11_1","doi-asserted-by":"publisher","DOI":"10.1039\/D5SC05819H"},{"key":"e_1_2_6_12_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jmedchem.3c02239"},{"key":"e_1_2_6_13_1","doi-asserted-by":"publisher","DOI":"10.1039\/D4RA05694A"},{"key":"e_1_2_6_14_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsmedchemlett.0c00093"},{"key":"e_1_2_6_15_1","first-page":"371","volume-title":"Synthetic Methods in Drug Discovery","author":"O'Neill B. 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