Total Synthesis of the Cytotoxic Guaipyridine Sesquiterpene Alkaloid (+)‐Cananodine

The enantiospecific total synthesis of the cytotoxic guaipyridine sesquiterpene alkaloid (+)‐cananodine ( 1 ) is described. A chiral pool/chiral auxiliary based approach is described for the synthesis of a key oxazolidinone intermediate. Subsequent key steps involve diastereoselective oxazolidinone allylation, cycloheptenylmethanol formation using ring‐closing olefin metathesis, microwave‐assisted decarboxylative Claisen rearrangement reaction, and use of a novel pyridine‐forming method.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)