The properties of polymers are governed by multi-level structural parameters, with tacticity being particularly critical for crystallization, thermal, and mechanical performance. Conventional approaches to modulate tacticity-such as tuning monomer enantiomeric excess or synthesizing distinct catalysts-are often complex and lack precise control. To address this challenge, we present a stereocontrol strategy by exploiting an enantiopure catalyst governed by an enantiomorphic site control (ESC) mechanism and polymeric exchange between the enantiomer pair. As a result, the enantiopure DiMeBiPh-BINOL-salen catalysts (R, R)-Y1 and (S, S)-Y1 were designed and demonstrated outstanding isoselectivity for the ROP of rac-BBL via the ESC mechanism. Their racemic pair rac-Y1 exhibited high syndioselectivity (Pr = 0.93) due to polymeric exchange. Ultimately, a series of P3HB products with streamlined tacticity (Pm: 0.07-0.90) was readily prepared by simply adjusting the enantiomeric excess (ee) values of the catalyst. A systematic investigation of the relationship between tacticity and material properties was performed. This work not only establishes an efficient and controllable route to tailor-made P3HB but also provides a scalable pathway for precise stereocontrol in polymer synthesis.
P(V)-stereogenic compounds show diverse biological properties and remain as a focal point in medicinal chemistry and agrochemicals. Traditional approaches to access enantioenriched P(V)-stereogenic molecules largely depend on chromatographic resolution, chiral auxiliaries, and/or the use of optically active starting...
Soumen Barik, S. Mukhopadhyay, Romin Gogoi et al.· ACS Catalysis· 0 citations
Developing new reagents is one efficient strategy for expanding accessible chemical space. Recently, gem-diborylalkanes have emerged as a versatile class of boron-containing reagents with broad reactivity. However, most gem-diborylalkanes are achiral due to the pair of identical boryl groups, which restricts their util...
Hong-Yi Tao, Zhong-Xing Huang, Hairong Lyu· Journal of the American Chem...· 0 citations
Poly(lactic-co-glycolic acid) (PLGA) is widely used in biomedical applications owing to its high biodegradability and biocompatibility. Although the ring-opening polymerization (ROP) of methyl glycolide (MeG) offers a route to synthesizing alternating PLGA, the comparable reactivity of its two electrophilic ring-open...
Hyunhee Lee, Seung Hyun Lee, Hooseung Lee et al.· ACS Catalysis· 0 citations
A stereoselective methodology for the synthesis of highly substituted spiropyrrolidines via synergistic catalysis was developed. The transformation is based on a cooperative catalytic system combining chiral phosphoric acid (CPA) catalysis with achiral palladium catalysis and proceeds through a formal [3+2] cycloadditi...
Michael Franc, Ivana Císařová, J. Veselý· Journal of Organic Chemistry· 0 citations
Metalloids bridge the properties of metals and nonmetals, creating unique opportunities in drug discovery. However, the potential of silicon- and germanium-containing scaffolds in organic synthesis and medicinal chemistry remain underexplored, largely owing to the lack of general stereocontrolled synthetic methods, p...
Qiang Tao, Yu-Juan Wang, Kai-Ge Lu et al.· Journal of the American Chem...· 1 citation
While the enantiomeric separation of β-nitroalcohols from racemic mixtures is paramount to the manufacture of enantiopure pharmaceuticals, developing chiral separation materials that resolve these compounds with both high enantioselectivity and broad substrate scope remains a massive challenge. Herein, we report a homo...
Ruo-Nan Wu, Yuyang Zhong, Si-Yu Tu et al.· Inorganic Chemistry· 0 citations
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