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Synthesis of a Leiodermatolide Analogue with a Dienyl Side Chain
Author(s) -
Reiss Anita,
Maier Martin E.
Publication year - 2018
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201800693
Subject(s) - chemistry , side chain , stereochemistry , lactone , ether , yield (engineering) , bond cleavage , silyl ether , anisole , derivative (finance) , cleavage (geology) , silylation , organic chemistry , catalysis , geotechnical engineering , fracture (geology) , economics , financial economics , engineering , metallurgy , polymer , materials science
We explored the possibility of attaching a side chain to a leiodermatolide fragment by forming the C18/C19 double bond via Julia/Kocienski olefination. This worked with a δ ‐lactone surrogate, the meta ‐anisole derivative 17 in reasonable yield to give the acyclic pentaene 32 . However, due to problems during cleavage of the silyl ether at the 15‐OH, the corresponding macrolactone could not be obtained. Instead, it was possible to convert enal 31 by Tebbe olefination to pentaene 37 . This compound could be converted to macrolactone 41 from where the side chain truncated leiodermatolide analogues 42 (9‐ O ‐carbamoyl) and 43 (7‐ O ‐carbamoyl) were obtained. Both isomers were moderately cytotoxic highlighting the importance of the side chain with the δ ‐lactone.