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There's A Fungus Among Us: Synthesis of Trichodermaketone A, a Polyketide With Antifungal Properties

Alan Marmelstein, Matt Straesser, Stephanie Baima


CHEM 431W: Department of Chemistry, The Pennsylvania State University, University Park, PA 16802

Overview
The Trichoderma genus comprises a wide range of fungal species that are found throughout the world,1 many of which have evolved antifungal and antimicrobial properties. This poster contains a proposed synthesis of Trichodermaketone A, one of four compounds isolated from pelagic fungus Trichoderma koningii in early 2010.2

Proposed Reaction Scheme

Completed Steps
Primary Route: 1. Glycosylation of ribose with methanol and PTSA.3 2. Silane Protection of 2 with potassium t-butoxide, [18]crown-6, and trimethoxy(phenyl)-silane. Alternate 1; Benzylidine Protection and Proof of Concept: 1. Benzylidene protection of D-ribose with benzaldehyde and cat. PTSA in DMF.4 2. Silane protection of D-Ribose with potassium t-butoxide, [18]crown-6, and trimethoxy(phenyl)-silane. 3. Condensation of 1,3-cyclohexanedione and benzylidene in CHCl3 with DBU.5 4. Silane deprotection of 2 with potassium fluoride in water.6

Alternate Syntheses

Alternate 2; Isopropyladine Variation: 1. Glycosylation: See Primary Route. 2. Isopropylidene protection of 2 in acetone with Na2SO4 and cat. PTSA.7 Note: Experiments were performed on D-ribose rather than L-ribose featured in route to due to budget restrictions.

Acknowledgements
Many thanks to Dr. Katherine Masters, Siddhartha Kumar, Brian DeBerdt, Sean Nunez, Tim McFadden, Linda Price and Michelle Brown for their help and support.
L F H, J K,I G

Spectra

References
1. Yedidia, I.; Benhamou, N.; Chet, I. Appl. Environ. Microbiol. 1999, 65, 1061-1070. 2. Song, F.; Dai, H.; Tong, Tang, Y.; Ren, B.; Chen, C.; Sun, N.; Liu X.; Bian, J.; Liu, M.; Gao, H.; Liu, H.; Chen, X.; Zhang, L. Trichoderma koningii. J. Nat. Prod. 2010, 73, 806-810. 3. Simon,E.; Cook, K.; Pritchard, M.; Stripe, W.; Bruch, M.; Bendinskas, K. J. Chem. Educ. 2010, 87, 739-741. 4. Protecting Groups, Kocienski, P.J.; Georg Thieme Verlag: New York; 2000. 5. Mal, D.; Pahari, P.; De, S. R. Tetrahedron 2007, 63, 11781-11792. 6. Terauchi, T.; Machido, S.; Komba, S. Tetrahedron Lett. 2010, 51, 1497-1499. 7. Migawa, M.T; Girardet, J.; Walker, J.A.; Koszalka, G.W.; Chamverlain, S.D.; Drach, J.C.; Townsend, L.B. J. Med. Chem. 1998, 41, 1242-1251.

A-C

C,D

Figure 1: 1H NMR Spectrum of Di-(1-O-Methyl-2,3-siloxy-D-ribofurano)-(phenyl)silane.

Figure 2: Mass Spectrum of Di-(1-O-Methyl-2,3-siloxy-D-ribofurano)-(phenyl)silane

Figure 3: 1H NMR Spectrum of Isopropylidene Intermediate

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