biostudies-literatureUnknown16(1)Xia YThe precise placement of thioester bonds into sequence-controlled polymers remains a grand challenge. Here, we demonstrate the versatile synthesis of sequence-controlled polymers from the step polymerization of cyclic thioanhydrides (A), diacrylates (B), and diols/diamines (C). In addition to easily accessible diverse monomers, the method is metal-free/catalyst-free, atom-economical, and wide in monomer scope, yielding 107 polymers with >90% yields and weight-average molecular weights of up to 175.4 kDa. The obtained polymers contain ABAC-type repeating units and precisely distributed in-chain thioester and ester (and amide) groups. The chemoselectivity of the polymerization is revealed by density functional theory calculations. The polymer library exhibits considerably tunable performanceNature communications1974https://www.ebi.ac.uk/biostudies/studies/S-EPMC11862183biostudies-literaturePrecise placement of thioester bonds into sequence-controlled polymers containing ABAC-type units.PMC11862183Xia YGu CZhang XZhang CSun YWang JShao TfalsePrecise placement of thioester bonds into sequence-controlled polymers containing ABAC-type units.The precise placement of thioester bonds into sequence-controlled polymers remains a grand challenge. Here, we demonstrate the versatile synthesis of sequence-controlled polymers from the step polymerization of cyclic thioanhydrides (A), diacrylates (B), and diols/diamines (C). In addition to easily accessible diverse monomers, the method is metal-free/catalyst-free, atom-economical, and wide in monomer scope, yielding 107 polymers with >90% yields and weight-average molecular weights of up to 175.4 kDa. The obtained polymers contain ABAC-type repeating units and precisely distributed in-chain thioester and ester (and amide) groups. The chemoselectivity of the polymerization is revealed by density functional theory calculations. The polymer library exhibits considerably tunable performance2025-01-01T00:00:00Z2025 Feb2025-04-05T14:39:08.083Z2025-04-05T14:39:08.083ZS-EPMC118621834000066210.1038/s41467-025-57208-8