Abstract
The concept of photoswitchable enediynes, which are stable in the dark but undergo efficient cycloaromatization reaction to produce p-benzyne diradical after irradiation with light of an appropriate wavelength, is discussed. Two novel methods for the generation of reactive enediyne compounds from thermally stable precursors have been developed. In the first approach, one of the triple bonds of cyclodeca-3-ene-1,5-diynes is replaced with cyclopropenone group. Cyclopropenone-containing enediyne precursors are unable to undergo cycloaromatization because the enediyne fragment is incomplete. Photolysis of cyclopropenones results in the efficient decarbonylation and the regeneration of a triple bond thus completing the enediyne π-system. The second method employs photo-Wolff reaction to achieve ring contraction of stable eleven-membered ring precursor enediynes. Benzannulated cyclic enediynes produced by the photodecomposition of enediyne precursor containing 2-diazo-1,3-diketones possess enolized β-ketoester fragment and undergo remarkably facile τ36o = 5 min - 3 h) Bergman cyclization. The generation of reactive enediyne was also achieved with NIR light by non resonant two-photon excitation.
Keywords: Enediyne, photochemistry, photomedicine, cyclopropenone, diazoketone
Current Topics in Medicinal Chemistry
Title: Towards Photoswitchable Enediyne Antibiotics: Single and Two-Photon Triggering of Bergman Cyclization
Volume: 8 Issue: 6
Author(s): Andrei Polukhtine, Grigori Karpov and Vladimir V. Popik
Affiliation:
Keywords: Enediyne, photochemistry, photomedicine, cyclopropenone, diazoketone
Abstract: The concept of photoswitchable enediynes, which are stable in the dark but undergo efficient cycloaromatization reaction to produce p-benzyne diradical after irradiation with light of an appropriate wavelength, is discussed. Two novel methods for the generation of reactive enediyne compounds from thermally stable precursors have been developed. In the first approach, one of the triple bonds of cyclodeca-3-ene-1,5-diynes is replaced with cyclopropenone group. Cyclopropenone-containing enediyne precursors are unable to undergo cycloaromatization because the enediyne fragment is incomplete. Photolysis of cyclopropenones results in the efficient decarbonylation and the regeneration of a triple bond thus completing the enediyne π-system. The second method employs photo-Wolff reaction to achieve ring contraction of stable eleven-membered ring precursor enediynes. Benzannulated cyclic enediynes produced by the photodecomposition of enediyne precursor containing 2-diazo-1,3-diketones possess enolized β-ketoester fragment and undergo remarkably facile τ36o = 5 min - 3 h) Bergman cyclization. The generation of reactive enediyne was also achieved with NIR light by non resonant two-photon excitation.
Export Options
About this article
Cite this article as:
Polukhtine Andrei, Karpov Grigori and Popik V. Vladimir, Towards Photoswitchable Enediyne Antibiotics: Single and Two-Photon Triggering of Bergman Cyclization, Current Topics in Medicinal Chemistry 2008; 8 (6) . https://dx.doi.org/10.2174/156802608783955700
DOI https://dx.doi.org/10.2174/156802608783955700 |
Print ISSN 1568-0266 |
Publisher Name Bentham Science Publisher |
Online ISSN 1873-4294 |
Call for Papers in Thematic Issues
Chemistry Based on Natural Products for Therapeutic Purposes
The development of new pharmaceuticals for a wide range of medical conditions has long relied on the identification of promising natural products (NPs). There are over sixty percent of cancer, infectious illness, and CNS disease medications that include an NP pharmacophore, according to the Food and Drug Administration. Since NP ...read more
Current Trends in Drug Discovery Based on Artificial Intelligence and Computer-Aided Drug Design
Drug development discovery has faced several challenges over the years. In fact, the evolution of classical approaches to modern methods using computational methods, or Computer-Aided Drug Design (CADD), has shown promising and essential results in any drug discovery campaign. Among these methods, molecular docking is one of the most notable ...read more
Drug Discovery in the Age of Artificial Intelligence
In the age of artificial intelligence (AI), we have witnessed a significant boom in AI techniques for drug discovery. AI techniques are increasingly integrated and accelerating the drug discovery process. These developments have not only attracted the attention of academia and industry but also raised important questions regarding the selection ...read more
From Biodiversity to Chemical Diversity: Focus of Flavonoids
Flavonoids are the largest group of polyphenols, plant secondary metabolites arising from the essential aromatic amino acid phenylalanine (or more rarely from tyrosine) via the phenylpropanoid pathway. The flavan nucleus is the basic 15-carbon skeleton of flavonoids (C6-C3-C6), which consists of two phenyl rings (A and B) and a heterocyclic ...read more
- Author Guidelines
- Graphical Abstracts
- Fabricating and Stating False Information
- Research Misconduct
- Post Publication Discussions and Corrections
- Publishing Ethics and Rectitude
- Increase Visibility of Your Article
- Archiving Policies
- Peer Review Workflow
- Order Your Article Before Print
- Promote Your Article
- Manuscript Transfer Facility
- Editorial Policies
- Allegations from Whistleblowers
- Announcements