Nazarov cyclization initiated by peracid oxidation: the total synthesis of (+/-)-rocaglamide.
The total syntheses of aglafolin, rocagloic acid, and rocaglamide using Nazarov cyclization are described. Generation of the necessary oxyallyl cation intermediate was accomplished via peracid oxidation of an allenol ether to generate an unusual oxycarbenium ion species that undergoes cyclization. The synthesis is efficient, highly diastereoselective, and strategically distinct from previous syntheses of rocaglamide.
Malona
John A
JA
Department of Chemistry, University of Rochester, Rochester, New York 14627, USA.
Cariou
Kevin
K
Frontier
Alison J
AJ
D001572:Benzofurans / Q000138:chemical synthesis*; D003500:Cyclization; D004852:Epoxy Compounds / Q000737:chemistry; D010084:Oxidation-Reduction; D013237:Stereoisomerism
D001572:Benzofurans; D004852:Epoxy Compounds; C107772:rocaglamide