Stereoselective total synthesis of hainanolidol and harringtonolide via oxidopyrylium-based [5 + 2] cycloaddition.
The tetracyclic carbon skeleton of hainanolidol and harringtonolide was efficiently constructed by an intramolecular oxidopyrylium-based [5 + 2] cycloaddition. An anionic ring-opening strategy was developed for the cleavage of the ether bridge in 8-oxabicyclo[3.2.1]octenes derived from the [5 + 2] cycloaddition. Conversion of cycloheptadiene to tropone was realized by a sequential [4 + 2] cycloaddition, Kornblum-DeLaMare rearrangement, and double elimination. The biomimetic synthesis of harringtonolide from hainanolidol was also confirmed.
School of Pharmacy, University of Wisconsin, Madison, Wisconsin 53705, USA.
Min
M
Zhang
Na
N
Liu
Weiping
W
Tang
D061565:Cycloaddition Reaction; D006248:Harringtonines / Q000138:chemical synthesis* / Q000737:chemistry*; D011714:Pyrans / Q000737:chemistry*; D013237:Stereoisomerism; D013379:Substrate Specificity
D006248:Harringtonines; D011714:Pyrans; C020752:hainanolide; C035056:hainanolidol