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We employed native chemical ligation to attach multiple copies of peptide\/miniprotein around a fixed multi\u2010armed thioester core in a one\u2010pot fashion, leading to the first\u2010generation multimers. Further, using a reverse thioether ligation strategy, we synthesized second\u2010generation branched homo\/hetero multimers. The reactions proceed under an aqueous environment that closely mimics physiological conditions, forming multimeric products with yields ranging from 30% to 90%. The general utility of this strategy is showcased by the synthesis of multimeric linear and bicyclic peptides, bicyclic peptide\u2010cell penetrating peptide conjugates, and multimeric miniproteins which show picomolar affinity against SARS\u2010CoV\u20102 receptor binding domain. We believe that this modular approach of generating multimeric molecules should find broad applicability in peptide chemistry and chemical biology.<\/jats:p>","DOI":"10.1002\/cbic.202500629","type":"journal-article","created":{"date-parts":[[2025,11,2]],"date-time":"2025-11-02T14:03:37Z","timestamp":1762092217000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Polyvalent Thioesters as Multifunctional Chemical Anchors: Toward Synthesis of Homo\/Hetero Peptide or Miniprotein Multimers"],"prefix":"10.1002","volume":"26","author":[{"given":"Arighna","family":"Sarkar","sequence":"first","affiliation":[{"name":"Tata Institute of Fundamental Research Hyderabad  36\/P Gopanpally Hyderabad Telangana 500046 India"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Sougat","family":"Das","sequence":"additional","affiliation":[{"name":"Tata Institute of Fundamental Research Hyderabad  36\/P Gopanpally Hyderabad 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