European Journal of Organic Chemistry
10.1002/ejoc.201600896
COMMUNICATION
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Scheme 8. Reaction of 1,7-enyne 1a with trimethylsilyldiazomethane in
different solvents. [a] The trans/cis diastereomeric ratio was determined by
1H NMR and corresponds to the relative configuration of the vinyl and ester
groups.
We have successfully opened a straightforward access to
the preparation of novel highly strained bicyclic pipecolic acid
derivatives via a one-step, atom-economical Cp*RuCl(cod)-
catalysed transformation of enynes. A variety of 1,7-enynes,
based on different -amino acids, with diversified scaffold
decoration, could lead to constrained analogues of natural
amino acid derivatives in good yields under mild conditions.
Good stereoselectivities for the created double bond were
observed, depending on the nature of the diazo compounds.
The last step of the catalytic cycle of this reaction involves a
constrained ruthenacyclobutane species which leads to two
diastereomers. The study of the diastereoselectivity implies that
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a
diastereoselectivity up to 90% could be obtained. Further studies
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Typical procedure for catalytic reaction: In a Schlenk tube under inert
atmosphere, to a solution of the enyne (1 mmol) in degassed diethy ether,
dioxane or methanol were added 1.1 mmol of
a
2.0
M
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trimethylsilyldiazomethane solution in diethyl ether or 3.0 mmol of
ethyldiazoacetate. 5 mol% of the precatalyst Cp*RuCl(cod) were then
introduced. The mixture was stirred at room temperature or at 100 °C for
2-3 h. The solvent was removed under vacuum and the diastereomers
were purified using standard chromatography over silica gel with a
diethylether/pentane eluting mixture.
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All procedures and characterisation data are presented in the Supporting
Information.
[17] CCDC 1483168 contains the supplementary crystallographic data for
this paper. These data can be obtained free of charge from the
Acknowledgements
Cambridge
Crystallographic
Data
Centre
via
The authors are grateful to the Region Bretagne through an
ARED program for a PhD grant to S.M.
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Keywords: amino acids • bicyclisation • diazoalkanes • enynes •
ruthenium
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