Development of a bio-inspired acyl-anion equivalent macrocyclization and synthesis of a trans-resorcylide precursor.
Studies on the macrocyclization of alpha,omega-dialdehydes have revealed a strong dependence on ring size with respect to the ultimate efficiency of the reaction. Strong catalyst dependence was observed, as thiazolium salts led to no detectable product formation, whereas electron-deficient triazolium salts served as precatalysts for the cyclization. Surprisingly, the N-pentafluorophenyl triazolium variant led to cyclization at room temperature within a short 90-min reaction time. These findings were applied to a range of substrates, including the synthesis of a key intermediate in a rapid synthesis of trans-resorcylide.
Mennen
Steven M
SM
Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467-3860, USA.
Miller
Scott J
SJ
D000215:Acylation; D000447:Aldehydes / Q000737:chemistry; D000838:Anions / Q000737:chemistry*; D018360:Crystallography, X-Ray; D003500:Cyclization; D004583:Electrons; D007536:Isomerism; D007659:Ketones / Q000737:chemistry; D018942:Macrolides / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure
D000447:Aldehydes; D000838:Anions; D007659:Ketones; D018942:Macrolides