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A novel metal-free and protecting-group-free synthesis method to prepare telechelic thiol-functionalized polyesters is developed by employing organocatalysis. A scope of Brønsted acids, including trifluoromethanesulfonic acid (1), HCl.Et2O (2), diphenyl phosphate (3), γ-resorcylic acid (4) and methanesulfonic acid (5), are evaluated to promote ring-opening polymerization of ε-caprolactone with unprotected 6-mercapto-1-hexanol as the multifunctional initiator. Among them, diphenyl phosphate (3) exhibits great chemoselectivity and efficiency, which allows for simply synthesis of thiol-terminated poly(ε-caprolactone) with near-quantitative thiol fidelity, full monomer conversion, controlled molecular weight and narrow polydispersity. Kinetic study confirms living/controlled nature of the organocatalyzed chemoselective polymerizations. Density functional theory calculation illustrates that the chemoselectivity of diphenyl phosphate (3) is attributed to the stronger bifunctional activation of monomer and initiator/chain-end as well as the lower energy in hydroxyl pathway than thiol one. Moreover, series of tailor-made telechelic thiol-terminated poly(δ-valerolactone) and block copolymers are efficiently generated under mild conditions.

Triphenylmethylium cation catalyzed Povarov reactions with excellent yields in 1 h with a remarkably low loading (0.5 mol %) are disclosed. A Lewis acidic carbenium catalysis mechanism was proposed and validated. A three-component Povarov reaction in a batch was transferred into a two-stage microflow process, which resulted in a 60-fold reduction in reaction time from 2 h to 2 min with 89% separated yield.