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

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

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Chiral Lewis Acid-Catalyzed Intramolecular [2 + 2] Photocycloaddition: Enantioselective Synthesis of Azaarene-Functionalized Azabicyclo[2.1.1]hexanes and Bicyclo[1.1.1]pentanes

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

Published: April 2, 2025

We present an asymmetric intramolecular [2 + 2] photocycloaddition reaction enabled by a dual catalyst system involving DPZ as photosensitizer and chiral Sc(III) complex, leading to azaarene-functionalized 2-azabicyclo[2.2.1]hexanes (aza-BCHs). The approach efficiently preventing racemization during subsequent nitrogen-deletion skeletal editing of aza-BCHs yield 2-substituted bicyclo[1.1.1]pentanes (BCPs). method achieves high ee broad substrate scope, including the successful formation all-carbon quaternary stereocenters. Furthermore, activation simple azaarene substrates Lewis acids in photocatalysis highlights notable contribution this field.

Language: Английский

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Strained spiro heterocycles as potential bioisosteres: an update on the synthesis of heteroatom-containing spiro[2.3]hexanes and spiro[3.3]heptanes

Chemical Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Developments in the synthesis and application of strained spiro heterocycles are discussed, given their potential as non-classical rigid three-dimensional bioisosteres drug development.

Language: Английский

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Catalyst-Controlled Regiodivergent Synthesis of Bicyclo[2.1.1]hexanes via Photochemical Strain-Release Cycloadditions

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

Published: April 23, 2025

Bicyclo[2.1.1]hexane is an emerging scaffold in various pharmaceutical settings, but the scarcity of approaches to target different regioisomers from a common starting material prevents targeting broader range chemical space. Herein, we demonstrate new design for photocatalyst-controlled regiodivergent synthesis this scaffold. Of particular interest that two distinct substitution patterns was achieved under photochemical conditions with catalyst control. This possible due activating group, N-methylimidazole, not only playing important role guiding divergent pathways also enabling transformation functional groups. Transient absorption spectroscopy discerned between mechanisms, as assignable bands consistent electron transfer and energy processes were distinctively observed, depending on identity photocatalyst.

Language: Английский

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Exploring Simple Drug Scaffolds from the Generated Database Chemical Space Reveals a Chiral Bicyclic Azepane with Potent Neuropharmacology

Journal of Medicinal Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 24, 2025

Language: Английский

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