The paper describes the synergistic protocol developed by combinatorial Henry and Nef reaction for the synthesis of 2-substituted pyrrolidine and piperidine alkaloids containing 1, 3- aminoketone and 1, 3-amino alcohol units. The utility of the protocol is demonstrated by asymmetric synthesis of 12 natural products of which asymmetric synthesis of (−)-N- methylpelletierine is presented for the first time. The one-carbon homologation described ...