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Total Synthesis of the Biphenyl Alkaloid (−)‐Lythranidine
Author(s) -
Gebauer Konrad,
Fürstner Alois
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201402550
Subject(s) - chemistry , isomerization , alkyne , metathesis , ruthenium , total synthesis , piperidine , propargyl alcohol , allyl alcohol , cycloisomerization , biphenyl , nitrile , alkaloid , acyclic diene metathesis , stereochemistry , catalysis , organic chemistry , polymerization , polymer
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.