Oct 2026· Journal of the American Chemical Society· Vol 148, pp. 47482-47490· 0 citations· 65 references
Abstract
Developing enzymatic strategies for diverse reaction manifolds is a major objective in modern biocatalysis. Here, we report the first biocatalytic asymmetric Johnson–Corey–Chaykovsky (JCC) cyclopropanation via DNA catalysis. Unlike conventional small-molecule catalysis, which largely favors trans-cyclopropane formation, DNA catalysis enables diastereoselective access to both cis- and trans-cyclopropanes with excellent enantiocontrol from a single catalytic system. The platform accommodates sulfur ylides as well as amide- and ester-derived sulfoxonium ylides. In particular, phenolic ester-derived sulfoxonium ylides exhibit exceptional cis-selectivity while maintaining excellent stereocontrol, overcoming a longstanding limitation of small-molecule-catalyzed asymmetric JCC reactions. Preliminary mechanistic studies are consistent with a DNA scaffold-mediated pathway that promotes cis-diastereomer formation. Together with its scalability under low catalyst loading, this work establishes a previously inaccessible biocatalytic variant of the JCC reaction and expands the scope of DNA catalysis for diastereoselective synthesis.
We herein report the design and synthesis of a class of 3,4-dihydro-monothiobinaphthol (3,4-H2-MTB)-derived bifunctional catalysts and their application in the asymmetric electrophilic C–H disulfuration of aza[5]helicenes. These catalysts feature a cooperative dual-activation motif: the thioether moiety acts as a Lew...
Ze-Long Li, Qing-Yun Cai, Yu-Xuan Huo et al.· ACS Catalysis· 0 citations
Highly diastereoselective 1,2-metalate rearrangements of α-haloalkylboronic esters that simultaneously construct contiguous stereogenic centers remain limited. Herein, we report a highly diastereoselective and stereospecific 1,2-metalate rearrangement of enantioenriched α-haloalkylboronic esters using gem-diborylalkane...
Gwanggyun Kim, Doyoon Kim, Seungcheol Han et al.· Journal of the American Chem...· 0 citations
The asymmetric synthesis of 1,4-dicarbonyl compounds bearing all-carbon quaternary stereocenters remains a significant challenge in organic synthesis. Herein, we report a photoredox/nickel dual-catalyzed tandem radical addition and oxidation protocol that directly converts β-keto esters and styrenes into enantioenriche...
Catalytic asymmetric electrophilic alkene functionalization provides a powerful strategy for the construction of complex chiral molecules. Despite significant progress in this field, the asymmetric functionalization of alkenes promoted by an electrophilic carbon species via an exo-cyclization mode remains a formidable...
Xiang Liu, Tian Zhao, Jun-Jie Li et al.· Journal of the American Chem...· 0 citations
Inherently chiral molecules generated by the curvature of planar frameworks represent an emerging class of three-dimensional chiral architectures, yet their catalytic asymmetric synthesis remains highly challenging. Herein, we report a Pd-catalyzed asymmetric Suzuki-Miyaura coupling for the efficient construction of in...
β-4′-Hydroxymethyl-deleted nucleosides are a class of four-carbon-sugar isonucleosides that possess significant research value in medicinal chemistry and artificial genetic polymer science. Nevertheless, current synthetic methodologies are hampered by several drawbacks, including poor diastereoselectivity, considerable...
