Nicolaou KC.
*
Petasis NA,
Zipkin RE,
Uenishi J.
University of Pennsylvania, Philadelphia, USA
The Endiandric Acid Cascade. Electrocyclizations in Organic Synthesis. 1. Stepwise, Stereocontrolled Total Synthesis of Endiandric Acids A and B.
J. Am. Chem. Soc. 1982;
104: 5555-5557
Nicolaou KC.
*
Petasis NA,
Uenishi J,
Zipkin RE.
The Endiandric Acid Cascade. Electrocyclizations in Organic Synthesis. 2. Stepwise, Stereocontrolled Total Synthesis of Endiandric Acids C–G.
J. Am. Chem. Soc. 1982;
104: 5557-5558
Nicolaou KC.
*
Zipkin RE,
Petasis NA.
The Endiandric Acid Cascade. Electrocyclizations in Organic Synthesis. 3. "Biomimetic" Approach to Endiandric Acids A-G. Synthesis of Precursors.
J. Am. Chem. Soc. 1982;
104: 5558-5560
Nicolaou KC.
*
Petasis NA,
Zipkin RE.
The Endiandric Acid Cascade. Electrocyclizations in Organic Synthesis. 4. Biomimetic Approach to Endiandric Acids A-G. Total Synthesis and Thermal Studies.
J. Am. Chem. Soc. 1982;
104: 5560-5562
Key words
endiandric acids - electrocyclization - Glaser coupling - Diels–Alder reaction - biomimetic synthesis
Significance
Nicolaou and co-workers describe the total synthesis of the endiandric acids. Their approach exploits a cascade of pericyclic reactions, which allow assembly of the carbon skeletons in one step. This pathway had been hypothesized to be the biosynthetic origin of these natural products.
Comment
Aldehyde C was chosen as a common intermediate for the synthesis of alkynes E and G. Glaser coupling, oxidation, and elimination results in the formation of dialkyne H. Partial reduction to polyolefin I results in a series of electrocyclizations and cycloadditions giving rise to the target structures.
