Enantioselective formal [4π+2σ] cycloaddition of bicyclobutanes with nitrones enabled by asymmetric Lewis acid catalysis DOI Creative Commons
Jian‐Jun Feng, Wen‐Biao Wu, Xue-Chun Yang

et al.

Research Square (Research Square), Journal Year: 2024, Volume and Issue: unknown

Published: June 18, 2024

Abstract The absence of catalytic asymmetric methods for synthesizing chiral (hetero)bicyclo[n.1.1]alkanes has hindered their application in new drug discovery. Here we demonstrate the achievability an polar cycloaddition BCB using a Lewis acid catalyst and bidentate chelating substrate, as exemplified by current enantioselective formal [4π+2σ] BCBs with nitrones. In addition to diverse incorporating acyl imidazole group or pyrazole moiety, wide array nitrones are compatible this catalysis, successfully assembling two congested quaternary carbon centers aza-trisubstituted center pharmaceutically important hetero-bicyclo[3.1.1]heptane product up 99% yield >99% ee.

Language: Английский

Taming Inert B–H Bond with Low Energy Light: A Near-Infrared Light-Induced Approach to Facile Carborane Cluster-Amino Acid Coupling DOI

Sheng‐Wen Xu,

Hongjian Zhang,

Jibo Zong

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 1, 2025

The selective functionalization of inert B–H bonds in carborane clusters has been a formidable challenge. Recent advances have witnessed such reactions through photoredox methods utilizing ultraviolet or visible light irradiation. However, high-energy sources often suffer from poor energy efficiency, limited substrate scope, undesired side reactions, and low scalability. Here, we present the first successful bond under low-energy near-infrared (NIR) using carborane-based electron donor–acceptor complex. Both photophysical investigations theoretical modeling reveal facile single-electron transfer cage to electron-deficient photocatalyst, generating radical NIR follow-up pathway enables direct coupling carboranes with amino acids oligopeptides, yielding diverse array carborane-functionalized oligopeptides. Beyond expanding known chemical space boron cluster derivatives, further demonstrate that imaging targeting capabilities could serve as promising multifunctional carriers for neutron capture therapy. Thus, via not only provides straightforward practical strategy synthetic chemistry but also lays foundation development next-generation boron-containing biomolecules advanced functional materials.

Language: Английский

Citations

0
Enantioselective formal [4π+2σ] cycloaddition of bicyclobutanes with nitrones enabled by asymmetric Lewis acid catalysis DOI Creative Commons
Jian‐Jun Feng, Wen‐Biao Wu, Xue-Chun Yang

et al.

Research Square (Research Square), Journal Year: 2024, Volume and Issue: unknown

Published: June 18, 2024

Abstract The absence of catalytic asymmetric methods for synthesizing chiral (hetero)bicyclo[n.1.1]alkanes has hindered their application in new drug discovery. Here we demonstrate the achievability an polar cycloaddition BCB using a Lewis acid catalyst and bidentate chelating substrate, as exemplified by current enantioselective formal [4π+2σ] BCBs with nitrones. In addition to diverse incorporating acyl imidazole group or pyrazole moiety, wide array nitrones are compatible this catalysis, successfully assembling two congested quaternary carbon centers aza-trisubstituted center pharmaceutically important hetero-bicyclo[3.1.1]heptane product up 99% yield >99% ee.

Language: Английский

Citations

0