A biomimetic approach to the rocaglamides employing photogeneration of oxidopyryliums derived from 3-hydroxyflavones.
A unified biomimetic approach to the aglain-forbaglin-rocaglamide classes of natural products is reported. The approach involves photogeneration of oxidopyryliums via excited-state intramolecular proton transfer (ESIPT) of 3-hydroxyflavones followed by [3+2] dipolar cycloaddition to the aglain core. An alpha-ketol (acyloin) rearrangement was employed to transform the aglain core to the rocaglamide framework. This approach was successfully used for the synthesis of the natural product (+/-)-methyl rocaglate.
Gerard
Baudouin
B
Department of Chemistry, Center for Chemical Methodology and Library Development, Boston University, Boston, Massachusetts 02215, USA.
Jones Ii
Guilford
G
Porco
John A
JA
D001572:Benzofurans / Q000138:chemical synthesis* / Q000378:metabolism; D040761:Biomimetic Materials / Q000138:chemical synthesis / Q000378:metabolism; D005419:Flavonoids / Q000737:chemistry* / Q000378:metabolism; D010777:Photochemistry; D011726:Pyridinium Compounds / Q000737:chemistry* / Q000378:metabolism
D001572:Benzofurans; D005419:Flavonoids; D011726:Pyridinium Compounds; C107772:rocaglamide; C041477:3-hydroxyflavone