The long term goal of this research is to determine the scope and limitations of the palladium-catalyzed cross-coupling of hypervalent siloxanes with allylic ester and aryl derivatives. This methodology could serve as an alternative to Stille and Suzuki coupling protocols that have several limitations in the field of natural product synthesis. In this study, the reactions of aryl, vinyl, and allyl siloxanes with a variety of substrates will be investigated. In addition, evaluation of new palladium catalysts for cross-couplings with aryl chlorides and the use of chiral ligands for an asymmetric version of the cross-coupling reaction will be undertaken. Once the scope of the coupling methodology has been determined, the siloxane methodology will be employed for the total synthesis of the antitumor antibiotic (+)-pancratastatin and the antimitotic agent (-)-colchicine.

National Institute of Health (NIH)
National Cancer Institute (NCI)
Research Project (R01)
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Medicinal Chemistry Study Section (MCHA)
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Lees, Robert G
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University of Maryland College Park
Schools of Earth Sciences/Natur
College Park
United States
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Shukla, Krupa H; DeShong, Philip (2008) Studies on the mechanism of allylic coupling reactions: a hammett analysis of the coupling of aryl silicate derivatives. J Org Chem 73:6283-91
Kadalbajoo, Mridula; Park, Juhee; Opdahl, Aric et al. (2007) Synthesis and structural characterization of glucopyranosylamide films on gold. Langmuir 23:700-7
Seganish, W Michael; DeShong, Philip (2006) Application of aryl siloxane cross-coupling to the synthesis of allocolchicinoids. Org Lett 8:3951-4
Shukla, Krupa H; Boehmler, Debra J; Bogacyzk, Suzanne et al. (2006) Application of palladium-catalyzed allylic arylation to the synthesis of a (+/-)-7-deoxypancratistatin analogue. Org Lett 8:4183-6
Seganish, W Michael; Handy, Christopher J; DeShong, Philip (2005) Efforts directed toward the synthesis of colchicine: application of palladium-catalyzed siloxane cross-coupling methodology. J Org Chem 70:8948-55
Seganish, W Michael; DeShong, Philip (2004) Application of directed orthometalation toward the synthesis of aryl siloxanes. J Org Chem 69:6790-5
Seganish, W Michael; DeShong, Philip (2004) Palladium-catalyzed cross-coupling of aryl triethylammonium bis(catechol) silicates with aryl bromides using microwave irradiation. Org Lett 6:4379-81
Manoso, Amy S; Ahn, Chuljin; Soheili, Arash et al. (2004) Improved synthesis of aryltrialkoxysilanes via treatment of aryl Grignard or lithium reagents with tetraalkyl orthosilicates. J Org Chem 69:8305-14
Seganish, W Michael; DeShong, Philip (2004) Preparation and palladium-catalyzed cross-coupling of aryl triethylammonium bis(catechol) silicates with aryl triflates. J Org Chem 69:1137-43
Riggleman, Shaundra; DeShong, Philip (2003) Application of silicon-based cross-coupling technology to triflates. J Org Chem 68:8106-9

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