Asymmetric synthesis of enantioenriched (+)-elaeokanine A.
The key transformation in the total synthesis of (+)-elaeokanine A was accomplished by asymmetric deprotonation of N-Boc pyrrolidine, followed by the reaction of the in situ generated enantioenriched stereogenic cuprate reagent with (E)-4-bromo-1-iodo-1-trimethylsilyl-1-butene with retention of configuration. N-Boc deprotection, followed by a one-pot olefin isomerization and intramolecular amine alkylation afforded a bicyclic vinyl bromide that was converted into (+)-elaeokanine A by sequential halogen metal exchange and reaction of the organolithium reagent with N-butanoylmorpholine.
Dieter
R Karl
RK
Department of Chemistry, Hunter Laboratory, Clemson University, Clemson, South Carolina 29634-0973, USA. dieterr@clemson.edu
Chen
Ningyi
N
D000475:Alkenes / Q000737:chemistry; D000478:Alkylation; D000588:Amines / Q000737:chemistry; D001643:Bridged Bicyclo Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D003300:Copper / Q000737:chemistry; D003500:Cyclization; D007212:Indolizines / Q000737:chemistry*; D008094:Lithium / Q000737:chemistry; D015394:Molecular Structure; D009025:Morpholines / Q000737:chemistry; D009942:Organometallic Compounds / Q000737:chemistry; D013237:Stereoisomerism; D014753:Vinyl Compounds / Q000737:chemistry
D000475:Alkenes; D000588:Amines; D001643:Bridged Bicyclo Compounds; D007212:Indolizines; D009025:Morpholines; D009942:Organometallic Compounds; D014753:Vinyl Compounds; C035094:indolizine; D003300:Copper; C003763:vinyl bromide; C037574:morpholine; D008094:Lithium