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Evolution of a Polyene Cyclization Cascade for the Total Synthesis of (−)‐Cyclosmenospongine
Author(s) -
Speck Klaus,
Magauer Thomas
Publication year - 2017
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.201605029
Subject(s) - polyene , stereocenter , total synthesis , chemistry , stereochemistry , cationic polymerization , enol ether , radical cyclization , organic chemistry , enantioselective synthesis , catalysis
We report a full account on the development of a unique cationic polyene cyclization for the total synthesis of the tetracyclic meroterpenoid (−)‐cyclosmenospongine. A highly convergent three‐component coupling strategy enabled rapid access to individual cyclization precursors that were tested for their reactivity. The successful transformation generates three rings and sets four consecutive stereocenters in a single operation proceeding in a highly efficient manner to give exclusively the trans ‐decalin framework. In addition, we found that the enol ether geometry and the relative configuration of C3 and C8 are crucial for the success of the polyene cyclization.