1357016-37-5Relevant academic research and scientific papers
Cycloaromatization protocol for synthesis of polysubstituted phenol derivatives: Method development and mechanistic studies
Spencer, William T.,Frontier, Alison J.
, p. 7730 - 7736 (2012/10/30)
The scope of the cycloaromatization of propargylic ethers was explored using operationally simple air- and moisture-insensitive conditions. Highly substituted phenol derivatives were obtained in high yields. Mechanistic experiments indicate that the reaction occurs by an electrocyclization followed by 1,3-proton transfer.
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.
