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Ring‐Closing Metathesis and Photo‐Fries Reaction for the Construction of the Ansamycin Antibiotic Kendomycin: Development of a Protecting Group Free Oxidative Endgame
Author(s) -
Magauer Thomas,
Martin Harry J.,
Mulzer Johann
Publication year - 2010
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200902226
Subject(s) - polyketide , ring closing metathesis , total synthesis , metathesis , stereochemistry , chemistry , ring (chemistry) , protecting group , double bond , chess endgame , salt metathesis reaction , combinatorial chemistry , organic chemistry , computer science , biosynthesis , alkyl , artificial intelligence , polymerization , enzyme , polymer
Two convergent total syntheses of the ansa ‐polyketide (−)‐kendomycin ( 1 ) are described. The syntheses benefit from the use of readily available and cheap starting materials. Highly complex diastereoselective Claisen–Ireland rearrangements were used to introduce the ( E )‐double bond and the C16‐Me group. The ring closure of the strained ansa macrocycle was achieved by ring‐closing metathesis and a highly efficient combination of macrolactonization and photo‐Fries reaction. A protecting group free endgame via an unstable o ‐quinone is presented. Additionally some unsuccessful synthetic efforts towards the total synthesis of 1 are described.