Coupling of alkenes and alkynes: synthesis of the C1-C11 And C18-C28 fragments of miyakolide.
A transition metal-mediated, atom-economical approach toward the crucial A and D rings of miyakolide is described. A Pd-catalyzed alkyne-alkyne coupling/6- endo- dig cyclization is employed to assemble the A ring fragment. The key D ring pyran is constructed utilizing an Ru-catalyzed alkene-alkyne coupling followed by a Pd-catalyzed allylic alkylation to establish the all-cis stereochemistry.
Trost
Barry M
BM
Department of Chemistry, Stanford University, Stanford, California 94305-5080, USA. bmtrost@stanford.edu
Ashfeld
Brandon L
BL
D000475:Alkenes / Q000737:chemistry*; D000478:Alkylation; D000480:Alkynes / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D018942:Macrolides / Q000138:chemical synthesis* / Q000737:chemistry; D008968:Molecular Conformation; D010165:Palladium / Q000737:chemistry; D012428:Ruthenium / Q000737:chemistry; D013237:Stereoisomerism
D000475:Alkenes; D000480:Alkynes; D018942:Macrolides; C529920:miyakolide; D010165:Palladium; D012428:Ruthenium