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A unified strategy for the synthesis of 7-membered-ring-containing Lycopodium alkaloids.
Lee, Amy S; Liau, Brian B; Shair, Matthew D.
Afiliación
  • Lee AS; Department of Chemistry and Chemical Biology, Harvard University , Cambridge, Massachusetts 02138, United States.
J Am Chem Soc ; 136(38): 13442-52, 2014 Sep 24.
Article en En | MEDLINE | ID: mdl-25152067
A unique subset of the Lycopodium alkaloid natural products share a 7-membered-ring substructure and may potentially arise from a common biosynthetic precursor. To both explore and exploit these structural relationships, we sought to develop a unified biosynthetically inspired strategy to efficiently access these complex polycyclic alkaloids through the use of a cascade sequence. In pursuit of these goals, the first total synthesis of (+)-fastigiatine (2) was accomplished via a series of cascade reactions; we describe herein a full account of our efforts. Insight from these endeavors led to critical modifications of our synthetic strategy, which enabled the first total syntheses of (-)-himeradine A (1), (-)-lycopecurine (3), and (-)-dehydrolycopecurine (4), as well as the syntheses of (+)-lyconadin A (5) and (-)-lyconadin B (6). Our approach features a diastereoselective one-pot sequence for constructing the common 7-membered-ring core system, followed by either a biomimetic transannular Mannich reaction to access himeradine A (1), lycopecurine (3), and dehydrolycopecurine (4) or an imine reduction for lyconadins A (5) and B (6). This strategy may potentially enable access to all 7-membered-ring-containing Lycopodium alkaloids and provides additional insight into their biosynthetic origin.
Asunto(s)

Texto completo: 1 Bases de datos: MEDLINE Asunto principal: Lycopodium / Alcaloides Idioma: En Revista: J Am Chem Soc Año: 2014 Tipo del documento: Article País de afiliación: Estados Unidos

Texto completo: 1 Bases de datos: MEDLINE Asunto principal: Lycopodium / Alcaloides Idioma: En Revista: J Am Chem Soc Año: 2014 Tipo del documento: Article País de afiliación: Estados Unidos