Hydroxyl-Assisted trans-Reduction of 1,3-Enynes: Application to the Formal Synthesis of (+)-Aspicilin

Sebastian Schaubach; Kenichi Michigami; Alois Fürstner

doi:10.1055/s-0035-1562381

Synthesis, Table of Contents

Synthesis 2017; 49(01): 202-208
DOI: 10.1055/s-0035-1562381

paper

Hydroxyl-Assisted trans-Reduction of 1,3-Enynes: Application to the Formal Synthesis of (+)-Aspicilin

Sebastian Schaubach

^aMax-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim/Ruhr, Germany

,

Kenichi Michigami

^aMax-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim/Ruhr, Germany

^bFaculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan Email: fuerstner@kofo.mpg.de

,

Alois Fürstner*

^aMax-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim/Ruhr, Germany

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Abstract

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Dedicated to Prof. Dieter Enders on the occasion of his 70^th birthday

Abstract

1,3-Enynes are hardly amenable to trans-hydrometalation reactions, because they tend to bind the standard ruthenium catalysts too tightly. However, catalysts comprising a [Cp*Ru–Cl] unit allow such compounds to be used, provided they contain an OH group next to the triple bond. This aspect is illustrated by a formal synthesis of the lichen-derived macrolide aspicilin. The required macrocyclic enyne precursor was formed by an efficient ring-closing alkyne metathesis reaction.

Key words

alkyne metathesis - enynes - hydrostannation - molybdenum alkylidynes - natural products - ruthenium - trans-reduction

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References

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