95125-08-9Relevant articles and documents
Total synthesis of (±)-rocaglamide via oxidation-initiated nazarov cyclization
Malona, John A.,Cariou, Kevin,Spencer, William T.,Frontier, Alison J.
, p. 1891 - 1908 (2012/04/23)
This article describes the evolution of a Nazarov cyclization-based synthetic strategy targeting the anticancer, antiinflammatory, and insecticidal natural product (±)-rocaglamide. Initial pursuit of a polarized heteroaromatic Nazarov cyclization to construct the congested cyclopentane core revealed an unanticipated electronic bias in the pentadienyl cation. This reactivity was harnessed in a successful second-generation approach using an oxidation-initiated Nazarov cyclization of a heteroaryl alkoxyallene. Full details of these two approaches are given, as well as the characterization of undesired reaction pathways available to the Nazarov cyclization product. A sequence of experiments that led to an understanding of the unexpected reactivity of this key intermediate is described, which culminated in the successful total synthesis of (+)-rocaglamide.
Nazarov cyclization initiated by peracid oxidation: The total synthesis of (±)-rocaglamide
Malona, John A.,Cariou, Kevin,Frontier, Alison J.
supporting information; experimental part, p. 7560 - 7561 (2009/10/17)
(Chemical Equation Presented) 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 oxycarbeniumion species that undergoes cyclization. The synthesis is efficient, hig hly diastereoselective, and strategically distinct from previous syntheses of rocaglamide.
