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Cover Picture: Novel Stereocontrolled Approach to syn‐ and anti‐ Oxepene–Cyclogeranyl trans ‐Fused Polycyclic Systems: Asymmetric Total Synthesis of (−)‐Aplysistatin, (+)‐Palisadin A, (+)‐Palisadin B, (+)‐12‐Hydroxy‐Palisadin B, and the AB Ring System of Adociasulfate‐2 and Toxicol A (Chem. Eur. J. 15/2004)
Author(s) -
Couladouros Elias A.,
Vidali Veroniki P.
Publication year - 2004
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Reports
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200490051
Subject(s) - intramolecular force , total synthesis , stereochemistry , chemistry , metathesis , ring (chemistry) , ring closing metathesis , polymerization , organic chemistry , polymer
The cover picture shows Poseidon, God of the Seas, standing in front of his temple at Cape Sounion, on a calm and warm Mediterranean summer night, under the illumination of fullmoon. His divine strength resembles that of olefin‐metathesis catalysts. Like his powerful hands holding the illustrated diene, Grubbs catalyst forces these terminal olefins to an intramolecular coupling, which results in the formation of the CC double bond met on the depicted marine natural products. By employing this coupling reaction, the complicated carbon framework of the presented molecules, found in the southern waters of Australia, China, Japan, and India as secondary metabolites of the red alga genus Laurencia and the sea hare Aplysia angasi , are synthesized within short and efficient pathways. The second‐generation ring‐closing metathesis catalyst works smoothly giving high yields, managing to overcome the severe strain of the trans–anti relative stereochemistry of the formed ring system. Similar carbon architecture also decorates another class of natural products found in the deep waters off Palau and Queensland among the metabolites of sea sponge Haliclona ( Adocia sp.). A famous member of this class of compounds is adociasulfate‐2, the first known agent to specifically interact with protein kinesin motors. The first synthesis of the cyclogeranyl–oxepane trans ‐fused ring system of adociasulfate‐2 together with the total synthesis of the molecules shown in the cover picture are presented by E. A. Couladouros and V. P. Vidali on p. 3822 ff.

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