Total Synthesis of the Biphenyl Alkaloid (−)-Lythranidine†
M. Sc. Konrad Gebauer
Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr (Germany)
Search for more papers by this authorCorresponding Author
Prof. Alois Fürstner
Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr (Germany)
Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr (Germany)Search for more papers by this authorM. Sc. Konrad Gebauer
Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr (Germany)
Search for more papers by this authorCorresponding Author
Prof. Alois Fürstner
Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr (Germany)
Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr (Germany)Search for more papers by this authorGenerous financial support by the Max-Planck-Gesellschaft and the Fonds der Chemischen Industrie is gratefully acknowledged. We thank C. Wirtz for excellent NMR support and M. Hebenbrock for assistance in the preparation of the building blocks.
Abstract
A sequence comprising a ring-closing alkyne metathesis of a propargyl alcohol derivative, followed by a ruthenium-catalyzed redox isomerization of the derived cycloalkyne and a transannular aza-Michael addition allowed the formation of the distinguishing piperidine-metacyclophane framework of the Lythraceum alkaloid lythanidine in a few high-yielding steps. This application attests to the excellent functional-group tolerance of a molybdenum alkylidyne complex endowed with triphenylsilanolate ligands, which enabled the macrocyclization even in the presence of protic functionalities, and thus illustrates the power of contemporary catalytic acetylene chemistry for target-oriented synthesis.
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