Gold-catalyzed highly enantioselective synthesis of axially chiral allenes.
Axially chiral allenes are synthesized from chiral propargylamines catalyzed by KAuCl4 in high yields (up to 93% yield) and excellent enantioselectivities (up to 97% ee) in CH3CN at 40 degrees C. The reaction has been applied to the synthesis of novel allene-modified artemisinin derivatives with the delicate endoperoxide moieties remaining intact. A tentative mechanism regarding gold(I)-catalyzed intramolecular hydride transfer was proposed on the basis of deuterium-labeling experiments and ESI-MS analysis of the reaction mixture.
Lo
Vanessa Kar-Yan
VK
Department of Chemistry and Open Laboratory of Chemical Biology of the Institute of Molecular Technology for Drug Discovery and Synthesis, The University of Hong Kong, Pokfulam Road, Hong Kong, China.
Wong
Man-Kin
MK
Che
Chi-Ming
CM
D000466:Alkadienes / Q000138:chemical synthesis* / Q000737:chemistry; D037621:Artemisinins / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D006046:Gold / Q000737:chemistry*; D015394:Molecular Structure; D010293:Pargyline / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D011437:Propylamines / Q000138:chemical synthesis / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization; D013237:Stereoisomerism
D000466:Alkadienes; D037621:Artemisinins; D011437:Propylamines; C009054:propargylamine; C025947:propadiene; D006046:Gold; D010293:Pargyline; C031327:artemisinin