Toró A,
Nowak P,
Deslongchamps P.
*
Université de Sherbrooke, Quebec, Canada
Transannular Diels–Alder Entry into Stemodanes: First Asymmetric Total Synthesis
of (+)-Maritimol.
J. Am. Chem. Soc. 2000;
122: 4526-4527
DOI:
10.1021/ja000728f
Key words
(+)-maritimol - diterpenoid - Takai reaction - Stille coupling - Appel reaction -
Dess–Martin oxidation - Diels–Alder reaction - Peterson olefination - Thorpe–Ziegler
reaction
Significance
In 2000, Deslongchamp and co-workers reported the first asymmetric total synthesis
of the diterpenoid (+)-maritimol. Key to their approach is a transannular Diels–Alder
(TADA) reaction.
Comment
Stille coupling of vinyl iodide E and stannane C, followed by Appel reaction gave access to acyclic tetraene G. Base-mediated macrocyclization, deprotection and oxidation furnished aldehyde I, which undergoes the desired TADA reaction and decarboxylation upon heating.
