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A simple and highly efficient approach to hydroxylated pyrrolizidine and indolizidine is developed from an aldehyde as a starting material using organocatalytic and asymmetric dihydroxylation reactions as key steps. Its application to the total synthesis of (−)-lentiginosine, (−)-epi-1,2-lentiginosine and (−)-dihydroxypyrrolizidine is also reported.

Graphical abstract: A stereoselective approach to indolizidine and pyrrolizidine alkaloids: total synthesis of (−)-lentiginosine, (−)-epi-lentiginosine and (−)-dihydroxypyrrolizidine

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