Convergent stereospecific total synthesis of monocillin I and radicicol: some simplifications and improvements

A much improved and reliable access to the macrolide 9 , key-intermediate in our synthesis of monocillin I and radicicol is reported, via a modification of our first synthesis. The formation of the conjugated E, Z-dienone trans-epoxide is now achieved in a much higher yield, in a stereospecific reac...

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Bibliographic Details
Published in:Tetrahedron letters 2002-05, Vol.43 (22), p.3997-4001
Main Authors: Tichkowsky, Isabelle, Lett, Robert
Format: Article
Language:English
Subjects:
coupling reactions
dienones
isocoumarins
macrolides
Mitsunobu reactions
tin and compounds
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Summary:A much improved and reliable access to the macrolide 9 , key-intermediate in our synthesis of monocillin I and radicicol is reported, via a modification of our first synthesis. The formation of the conjugated E, Z-dienone trans-epoxide is now achieved in a much higher yield, in a stereospecific reaction, by elimination of the methanesulfonate ester of the 6′-OH of the intermediate macrolide. It is also shown that the configuration of the 6′-OH has no significant incidence on all the steps leading to 9 , and that consequently the two diastereoisomers 12 , epimeric at 6′, can be used for the synthesis of radicicol. The stereospecific formation of the key-intermediate macrolide having the desired conjugated E, Z-dienone trans-epoxide has been achieved in a much higher yield, via a modification of our first synthesis. The configuration at 6′ of the intermediates is also shown to have no significant incidence on all the steps of the sequence.
ISSN:0040-4039
1873-3581
DOI:10.1016/S0040-4039(02)00713-X