Photochemical 1,3‐Acyl Shifts in Natural Product Synthesis

Lübken, Dennis; Siekmeyer, Björn; Kalesse, Markus

doi:10.1002/ejoc.202200701

Cited by 2 publications

(1 citation statement)

References 44 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…1E ) ( 19 ). Undoubtedly, photochemical 1,2-acyl and 1,3-acyl migrations represent a powerful tool to construct various polycyclic carbon backbones of complex natural products ( 20 – 23 ). To the best of our knowledge, photoinduced C → C intramolecular 1,4-acyl migration has never been reported.…”

Section: Introductionmentioning

confidence: 99%

UV light–driven late-stage skeletal reorganization to diverse limonoid frameworks: A proof of concept for photobiosynthesis

Jiang

et al. 2023

Sci. Adv.

View full text Add to dashboard Cite

Late-stage skeletal reorganization (LSSR) is a type of fascinating organic transformation processes in natural product total synthesis. However, few facile and effective LSSR methodologies have hitherto been developed. Here, LSSR of limonoid natural products via photochemical cascades is first reported. Starting from xyloelves A and B, nine distinct limonoid products with five unprecedented scaffolds are generated. The photocascade pathways of these natural products and mechanistic rationale via intramolecular triplet energy transfer are revealed by quantum mechanical calculations. Most notably, ultraviolet light–driven transannular and stereoselective C → C 1,4-acyl migration is first found as a photochemical approach, particularly for LSSR of natural products. This approach holds promise for designing LSSR strategies to access bioactive cage-like molecules. Besides that, our findings provide a clear proof of concept for natural product photobiosynthesis. Xyloelf A, substantially ameliorating concanavalin A–induced liver injury in mice, could be used as a unique molecular template for hepatoprotective drug discovery.

show abstract

Section: Introductionmentioning

confidence: 99%

UV light–driven late-stage skeletal reorganization to diverse limonoid frameworks: A proof of concept for photobiosynthesis

Jiang

et al. 2023

Sci. Adv.

View full text Add to dashboard Cite

show abstract

Unlocking Photocycloaddition Reactivity of Tropolone by Cage-Confined Visible-Light Photocatalysis for Multilevel Selective Transformation

Chen,

Huang,

Yang

et al. 2024

J. Am. Chem. Soc.

View full text Add to dashboard Cite

The precise asymmetric photochemical transformation of organic compounds containing multiple reactive sites presents significant progress in synthetic chemistry. Herein, we report an unprecedented visible-light-induced cascade transformation of tropolone cyclic triene derivatives by using chiral photoactive metal−organic cages (cPMOCs) as enzyme-mimicking multipocket photocatalysts. The cage-confined photocatalysis promotes three successive elementary steps, i.e., enantioselective [2 + 2] photocycloaddition with chalcone, regio-, and diastereoselective α-ketol rearrangement, and a stereoselective 1,3-acyl shift, resulting in bicyclo[3.2.2]nonane skeleton with multichiralcenters unattainable by other methods. This study demonstrates how complex synthetic challenges of peri-, chemo-, and stereoselectivities could be subtly manipulated by cage-confined supramolecular catalysis for exploration of new reactivities.

show abstract

Photochemical 1,3‐Acyl Shifts in Natural Product Synthesis

Abstract: Dedicated to Prof. Cesare Gennari on the occasion of his 70th birthday.

Cited by 2 publications

References 44 publications

UV light–driven late-stage skeletal reorganization to diverse limonoid frameworks: A proof of concept for photobiosynthesis

UV light–driven late-stage skeletal reorganization to diverse limonoid frameworks: A proof of concept for photobiosynthesis

Unlocking Photocycloaddition Reactivity of Tropolone by Cage-Confined Visible-Light Photocatalysis for Multilevel Selective Transformation

Contact Info

Product

Resources

About