Enantioselective synthesis of 9 desmethylgarugamblin i
1 / 13

Enantioselective Synthesis of 9’-Desmethylgarugamblin I - PowerPoint PPT Presentation

  • Uploaded on

Enantioselective Synthesis of 9’-Desmethylgarugamblin I. Andrew Willeford Dr. Christopher M. Beaudry Department of Chemistry HHMI 2009. Natural Products. Opium Poppy. Penicillum Fungi. Chromodoris macfarlandi. Morphine. Penicillin. Macfarlandin E.

I am the owner, or an agent authorized to act on behalf of the owner, of the copyrighted work described.
Download Presentation

PowerPoint Slideshow about ' Enantioselective Synthesis of 9’-Desmethylgarugamblin I' - ford

An Image/Link below is provided (as is) to download presentation

Download Policy: Content on the Website is provided to you AS IS for your information and personal use and may not be sold / licensed / shared on other websites without getting consent from its author.While downloading, if for some reason you are not able to download a presentation, the publisher may have deleted the file from their server.

- - - - - - - - - - - - - - - - - - - - - - - - - - E N D - - - - - - - - - - - - - - - - - - - - - - - - - -
Presentation Transcript
Enantioselective synthesis of 9 desmethylgarugamblin i

Enantioselective Synthesis of 9’-Desmethylgarugamblin I

Andrew Willeford

Dr. Christopher M. Beaudry

Department of Chemistry

HHMI 2009

Natural products
Natural Products 9’-Desmethylgarugamblin I

Opium Poppy

Penicillum Fungi




Macfarlandin E

Diaryl ether heptanoids
Diaryl 9’-Desmethylgarugamblin I Ether Heptanoids

  • Exhibit useful biological activities

    • Anti-inflammatory

    • Anticancer

    • Antibacterial

  • General structure

    • Seven carbon chain tethered

      together by a diaryl ether


    • Cyclophanes

Optical activity
Optical Activity 9’-Desmethylgarugamblin I

  • 17 diaryl ether heptanoids do not possess stereocenters

    • Six of these 17 compounds are chiral by virtue of their tethered-ring structure and have been isolated as optically active compounds.

  • Planar chirality

    • Mobius Strip

This work is licensed under a Creative Commons Attribution-Share Alike 3.0 Unported License.

Question 9’-Desmethylgarugamblin I

  • These compounds are almost identical to each other

    • Minimal difference in substituents

    • Why such a difference in optical rotation?

Isolation 9’-Desmethylgarugamblin I

  • All 17 compounds were isolated from plant sources

    • 9’-desmethylgarugamblin I is a bark extract of Garugapinnata

      • A frankencense

      • Found in Asia

      • Used in folk medicine

  • Typical isolation

    • Includes extraction in a Soxhlet

      apparatus at high temperatures

Hypothesis 9’-Desmethylgarugamblin I

  • Isolation of these compounds have led to racemization

    • Enantioselective synthesis of 9’-desmethylgarugamblin I would allow verification of our hypothesis

    • Will offer proof of concept to enantioselectively synthesize the compounds with non-reported optical rotations

Enantioselectivity 9’-Desmethylgarugamblin I

  • Selective synthesis of one enantiomer

  • Pathway

    • Cu catalyst on non-racemic, chiralligands promotes the enantioselective synthesis of 9’-desmethylgarugamblin I

Chiral catalysts
Chiral 9’-Desmethylgarugamblin I Catalysts

  • A catalyst with enantiomeric forms

    • Holds substrate in specific conformation

    • Lowers energy barrier for formation of one enantiomer

  • Examples

    • Walphos

    • Naud

    • Josiphos

    • Enzymes

Mechanistic considerations
Mechanistic Considerations 9’-Desmethylgarugamblin I

Progress 9’-Desmethylgarugamblin I

Future research
Future Research 9’-Desmethylgarugamblin I

  • Enantioselective synthesis of other aryl ethers

Acknowledgements 9’-Desmethylgarugamblin I

  • Howard Hughes Medical Institute

  • Undergraduate Research, Innovation, Scholarship, & Creativity (URISC) Program

  • Dr. Christopher M. Beaudry

  • Dr. Kevin Ahern