Total synthesis and structural elucidation of azaspiracid-1 : construction of key building blocks for originally proposed structure

Nicolaou, K. C., Pihko, Petri M., Bernal, Federico, Frederick, Michael O., Qian, Wenyuan, Uesaka, Noriaki, Diedrichs, Nicole, Hinrichs, Jürgen, Koftis, Theocharis V., Loizidou, Erika, Petrovic, Goran, Rodriquez, Manuela, Sarlah, David and Zou, Ning (2006) Total synthesis and structural elucidation of azaspiracid-1 : construction of key building blocks for originally proposed structure. Journal of the American Chemical Society, 128 (7) . pp. 2244-2257. ISSN 0002-7863 (doi:10.1021/ja0547477)

Abstract

Syntheses of the three key building blocks (65, 98, and 100) required for the total synthesis of the proposed structure of azaspiracid-1 (1a) are described. Key steps include a TMSOTf-induced ring-closing cascade to form the ABC rings of tetracycle 65, a neodymium-catalyzed internal aminal formation for the construction of intermediate 98, and a Nozaki−Hiyama−Kishi coupling to assemble the required carbon chain of fragment 100. The synthesized fragments, obtained stereoselectively in both their enantiomeric forms, were expected to allow for the construction of all four stereoisomers proposed as possible structures of azaspiracid-1 (1a−d), thus allowing the determination of both the relative and absolute stereochemistry of the natural product.

Item Type: Article
Research Areas: A. > School of Science and Technology > Natural Sciences
Item ID: 14366
Depositing User: Erika Loizidou
Date Deposited: 06 Mar 2015 10:44
Last Modified: 13 Oct 2016 14:32
URI: https://eprints.mdx.ac.uk/id/eprint/14366

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