Stereoconvergent Chain-Growth Polymerization DOI Creative Commons
Jake R. Jagannathan, Frank A. Leibfarth

ACS Central Science, Год журнала: 2025, Номер 11(5), С. 797 - 804

Опубликована: Май 5, 2025

The stereochemistry of polymers has a profound impact on their properties. Despite the well-developed stereoselective methods for prochiral vinyl monomers, current racemic monomers are limited. Conventional approaches treat sp 3 chiral centers as immutable, resulting in poor atom-economical processes and limited control over enantioselectivity. This contrasts with stereoconvergent catalysis small molecules, which revolutionized synthesis by interrupting transfer information from substrate to product, providing clear platform catalysts access enantiopure compounds mixtures up 100% yield. Here we designed catalyst that converges stereochemical during polymerization, enabling asymmetric, isotactic quantitative atom economy feedstocks. mechanism stereoconvergence is accomplished ablating information, followed propagation event both tacticity Using this method, accessed enantiomers an polymer single enantiomer monomer identified novel stereocomplex. These results represent conceptual framework expand polymerization into additional mechanisms.

Язык: Английский

Copper-Catalyzed Asymmetric Nucleophilic Opening of 1,1,2,2-Tetrasubstituted Donor–Acceptor Cyclopropanes for the Synthesis of α-Tertiary Amines DOI

Shouang Lan,

Qinqin Cui,

Defu Luo

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Дек. 26, 2024

Catalytic asymmetric transformation of donor–acceptor cyclopropanes (DACs) has been proven to be a highly valuable and robust strategy construct diverse types enantioenriched molecules. However, the use 1,1,2,2-tetrasubstituted DACs form products bearing quaternary stereocenters remains long-term unsolved challenge. Here, we report copper-catalyzed aminative ring opening tetrasubstituted alkynyl that delivers myriad α-tertiary amines with high levels enantioselectivities. The alkyne, amine, ester moieties within enable further applications, including synthesis bioactive Mechanistic studies indicate zwitterionic intermediate copper-acetylide unit plays key role in process, which represents new mode for achieving catalytic DACs.

Язык: Английский

Процитировано

3
Ligand-enabled override of the memory effect in Rh-catalyzed asymmetric Suzuki reactions DOI Creative Commons
Ke Liu, David Egea‐Arrebola, Ruchuta Ardkhean

и другие.

Chem, Год журнала: 2025, Номер unknown, С. 102550 - 102550

Опубликована: Апрель 1, 2025

Язык: Английский

Процитировано

0
Stereoconvergent Chain-Growth Polymerization DOI Creative Commons
Jake R. Jagannathan, Frank A. Leibfarth

ACS Central Science, Год журнала: 2025, Номер 11(5), С. 797 - 804

Опубликована: Май 5, 2025

The stereochemistry of polymers has a profound impact on their properties. Despite the well-developed stereoselective methods for prochiral vinyl monomers, current racemic monomers are limited. Conventional approaches treat sp 3 chiral centers as immutable, resulting in poor atom-economical processes and limited control over enantioselectivity. This contrasts with stereoconvergent catalysis small molecules, which revolutionized synthesis by interrupting transfer information from substrate to product, providing clear platform catalysts access enantiopure compounds mixtures up 100% yield. Here we designed catalyst that converges stereochemical during polymerization, enabling asymmetric, isotactic quantitative atom economy feedstocks. mechanism stereoconvergence is accomplished ablating information, followed propagation event both tacticity Using this method, accessed enantiomers an polymer single enantiomer monomer identified novel stereocomplex. These results represent conceptual framework expand polymerization into additional mechanisms.

Язык: Английский

Процитировано

0