Evaluation of (+)-sparteine-like diamines for asymmetric synthesis.
Three new (+)-sparteine-like diamines were prepared from (-)-cytisine and evaluated as sparteine surrogates in the alpha-lithiation rearrangement of cyclooctene oxide and the palladium(II)/diamine catalyzed oxidative kinetic resolution of 1-indanol. The new diamines exhibited opposite enantioselectivity to that observed with (-)-sparteine but increasing the steric hindrance of the N-alkyl group beyond N-Et had a detrimental effect on enantioselectivity. The optimal N-Me diamine was evaluated with much success in five other (-)-sparteine-mediated processes involving different metals (lithium, magnesium, and copper) and different types of reaction mechanisms.
Dearden
Michael J
MJ
Department of Chemistry, University of York, Heslington, York YO10 5DD, United Kingdom.
McGrath
Matthew J
MJ
O'Brien
Peter
P
D000470:Alkaloids / Q000737:chemistry*; D001392:Azocines / Q000737:chemistry*; D002384:Catalysis; D003959:Diamines / Q000138:chemical synthesis* / Q000737:chemistry*; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010165:Palladium / Q000737:chemistry; D011807:Quinolizines / Q000737:chemistry*; D013034:Sparteine / Q000138:chemical synthesis* / Q000737:chemistry*; D013237:Stereoisomerism; D000093843:Quinolizidine Alkaloids
D000470:Alkaloids; D001392:Azocines; D003959:Diamines; D010165:Palladium; D011807:Quinolizines; D013034:Sparteine; C004712:cytisine; D000093843:Quinolizidine Alkaloids