Synthesis of the unique angular tricyclic chromone structure proposed for aspergillitine, and its relationship with alkaloid TMC-120B†
Sebastián O. Simonetti,Enrique L. Larghi,Andrea B. J. Bracca,Teodoro S. Kaufman
Organic & Biomolecular Chemistry Pub Date : 03/19/2012 00:00:00 , DOI:10.1039/C2OB25067E
Abstract

The synthesis of the tricyclic angular chromone structure originally assigned to aspergillitine is reported. The synthesis was achieved in 11 steps and 15% overall yield from 2,4-dihydroxypropiophenone, through the intermediacy of 2,3-dimethyl-7-hydroxychromen-4-one. Construction of the nitrogen-bearing heterocyclic ring entailed a Stille cross-coupling reaction with n-Bu3SnCH2CH[double bond, length as m-dash]CH2, followed by double bond isomerization, oximation of the chromone carbonyl, and a final microwave-assisted electrocyclization of the thus formed 6π-electron aza-triene system.

Graphical abstract: Synthesis of the unique angular tricyclic chromone structure proposed for aspergillitine, and its relationship with alkaloid TMC-120B