RESUMEN
Condensation of 2H-benzo[g][1,2]oxasilocines with aromatic aldehydes in the presence of boron trifluoride affords mixtures of cis/trans 2-phenyl-3-vinylchromans with moderate yields. These can be transformed into homopterocarpans, a synthetic group of substances homologous to the natural isoflavonoid pterocarpans.
RESUMEN
A new strategy for the diastereoselective and convergent synthesis of pterocarpans which is able to control the relative stereochemistry of the molecule through allylation of aromatic aldehydes with cyclic allylsiloxanes is described.
Asunto(s)
Pterocarpanos/síntesis química , Aldehídos/química , Compuestos Alílicos/química , Cristalografía por Rayos X , Modelos Moleculares , Estructura Molecular , Pterocarpanos/química , Siloxanos/química , EstereoisomerismoRESUMEN
The total synthesis of natural pterocarpans and analogs is reviewed.
Asunto(s)
Pterocarpanos/síntesis química , Biomimética , CiclizaciónRESUMEN
The condensation of 2,3-dihydrobenzoxasilepins with aromatic aldehydes in the presence of boron trifluoride to form 2,3-dihydrobenzofurans shows a level of diastereoselection which is a function of the electronic nature of the aldehyde and the polarity of the solvent. The study of the mechanism of the reaction demonstrated that it proceeds through a ring-opened allylfluorosilane, which is stable enough to be isolated and characterized.
RESUMEN
2,3-Dihydrobenzofurans can be diastereoselectively prepared by condensation of aromatic aldehydes with 2,3-dihydrobenzoxasilepines under the catalysis of Ag(I) complexes, and in the presence of a source of fluoride ion. The application of this strategy by using chiral catalysts leads to a new enantioselective total synthesis of natural cis-pterocarpans and their trans isomers. Through this method, the first enantioselective total synthesis of the antifungal agent (-)-pterocarpin was achieved. In addition, a new entry into the heteroaromatic system of 2,5-dihydrobenzoxepine is also presented.