Total Synthesis of (+)-Cyanthiwigin U

Keywords

(+)-cyanthiwigin U - alkene cross-metathesis - Diels–Alder reaction - Swern oxidation - Grignard reaction - Dess–Martin oxidation - ring-closing metathesis - ring-opening metathesis - Babler–Dauben oxidation

Significance

Phillips and Pfeiffer reported the first enantioselective total synthesis of the cyathin diterpenoid ( + )-cyanthiwigin U and confirmed its absolute configuration. Their strategy relied on a tandem ring-opening/ring-closing metathesis of bicyclo[2.2.2]octene I to furnish the tricyclic skeleton of (+)-cyanthiwigin U.

 

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Comment

Diels–Alder reaction of enone D with diene E, followed by oxidative removal of the auxiliary, afforded carboxylic acid G as a single diastereomer. Regioselective reduction of J with LiAlH₄ (dr = 10:1), followed by 1,2-addition and Babler–Dauben oxidation of the resulting allylic tertiary alcohol furnished enone K.

 

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Publication History

Article published online:
27 August 2025