Formal Synthesis of (+)-Lasubine II and (−)-Subcosine II via Organocatalytic Michael Addition of a Ketone to an α-Nitrostyrene

Abstract

The first examples of an organocatalytic Michael addition of a ketone to in situ generated α-nitrostyrenes are reported. A suitably functionalized γ-nitroketone obtained from the organocatalyzed Michael addition was converted into (+)-2-epi-lasubine II, the immediate synthetic precursor of (+)-lasubine II and (-)-subcosine II (enantiomers of the natural quinolizidine alkaloids). Two of the three stereocenters in (+)-2-epi-lasubine II are set by the Michael reaction.