Total Synthesis of a Stereoisomer of Bistramide C and Assignment of Configuration of the Natural Product

Integrated approaches to the configurational assignment of marine natural products

“…This approach was used in the absolute stereoassignment of the bistramides (section 7.5). cxv Calculated molar rotations complement the UDB approach, but have another limitation. In absence of independent measurements of the [α] D of the natural product, the method largely rests on trust and reliance that the reported literature values were measured accurately on very pure samples; a condition that, regrettably, has not always prevailed.…”

“…cxv Wipf’s strategy synthesized the three stereosegments of bistramide C and analysis of their contributions to the molar rotation of the natural product.…”

Tris(methylthio)methane

“…38-42 Among total synthesis applications, 1 was used to homologate a primary triflate as a key step in the synthesis of a stereoisomer of bistramide C (eq 7) 15. Addition of 1, or better, the derived dichlorocerate, (MeS) 3 CCe Cl 2 , to a hindered and easily enolizable cyclohexanone was used as a component of a reductive carboxylation sequence in the synthesis of the diterpene dendrillol-1 (eq 9).…”

News: Angew. Chem. Int. Ed. 8/2003

“…Besides heterocyclic, organometallic, and combinatorial chemistry, the research of his group is focused on total syntheses of marine natural products; an example thereof is the "Total Synthesis of a Stereoisomer of Bistramide C and Assignment of Configuration of the Natural Product." [3] Their development of zirconium-based organome-tallic methods is summarized in a recent Concept entitled "Novel Applications of Alkenyl Zirconocenes". [4] Angewandte will publish a review on the "Chemistry and Biology of Biosynthetic Diels-Alder Reactions" by Williams in the near future.…”