Asymmetric synthetic access to the hetisine alkaloids: total synthesis of (+)-nominine.
A dual cycloaddition strategy for the synthesis of the hetisine alkaloids has been developed, illustrated by a concise asymmetric total synthesis of (+)-nominine (7). The approach relies on an early-stage intramolecular 1,3-dipolar cycloaddition of a 4-oxido-isoquinolinium betaine dipole with an ene-nitrile dipolarophile. Subsequent late-stage pyrrolidine-induced dienamine isomerization/Diels-Alder cascade allows for rapid construction of the carbon--nitrogen polycyclic skeleton within this class of C(20)-diterpenoid alkaloids.
Department of Chemistry, University of Illinois, Urbana, IL 61801, USA.
Kevin M
KM
Peese
David Y
DY
Gin
D000470:Alkaloids / Q000138:chemical synthesis*; D000588:Amines / Q000737:chemistry; D001622:Betaine / Q000737:chemistry; D001688:Biological Products / Q000138:chemical synthesis*; D001952:Bridged-Ring Compounds / Q000138:chemical synthesis*; D002244:Carbon / Q000737:chemistry; D004224:Diterpenes / Q000138:chemical synthesis*; D007211:Indoles / Q000138:chemical synthesis*; D007536:Isomerism; D007546:Isoquinolines / Q000737:chemistry; D008956:Models, Chemical; D009570:Nitriles / Q000737:chemistry; D009584:Nitrogen / Q000737:chemistry; D011083:Polycyclic Compounds / Q000737:chemistry; D011759:Pyrrolidines / Q000737:chemistry; D013237:Stereoisomerism
D000470:Alkaloids; D000588:Amines; D001688:Biological Products; D001952:Bridged-Ring Compounds; D004224:Diterpenes; D007211:Indoles; D007546:Isoquinolines; D009570:Nitriles; D011083:Polycyclic Compounds; D011759:Pyrrolidines; C473425:nominine; D001622:Betaine; D002244:Carbon; C032519:pyrrolidine; D009584:Nitrogen