Synthesis and absolute configuration of hyperaspine, an alkaloid of the ladybird Hyperaspis campestris

Hyperaspine, isolated from the European Coccinellidae Hyperaspis campestris, is the first representative of a new type of ladybird alkaloids having a 3-oxaquinolizidine skeleton. A new total synthesis of (+/-)-hyperaspine starting from protected piperidin-4-one has been achieved. The absolute configuration of the natural alkaloid was unequivocally established to be 3S,4aS,6R,8S by HPLC analyses on a chiral column.