Stereoselectrve totol synthesis of (f)-cubitene, o diterpane isolated from termite soldiers, and its stereoisomer has been achieved util rzing the anion-induced intramolecular cyclization.
Synthesis of macrocyclic terpenoids by intramoleclar cyclization II germaclane-type sesquiterpenes
✍ Scribed by Mitsuaki Kodama; Yasuo Matsuki; Shô Itô
- Publisher
- Elsevier Science
- Year
- 1976
- Tongue
- French
- Weight
- 192 KB
- Volume
- 17
- Category
- Article
- ISSN
- 0040-4039
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✦ Synopsis
In the previous paper (l), we hove described the biogenetic-type synthesis of diterpenes with a fourteen-membered ring, cembrene-A and nephthenol, exemplifying usefulness of the anion-induced intramolecular cyclizarion in the synthesis of macrocyclic terpenoids. We have applied the general reaction sequence to the synthesis of sesquiterpenes, where this type of cyclization is more important biogenetic pathway than in diterpenes. This communicarion deals with a convenient and highly selective synthesis of sesquiterpenes with ten-membered ring which would be quite laborious to construct by other methods (2).
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## Recently, we have reported the successful synthesis of natural hedycaryal l\_ (PE,6E-isomer) and 2Z,6E-'0) 1') '2)
The methyl ester of f+)-ceriferic acid-I, a 14-membered ring sesterterpene isolated from the wax of the scale insect Ceroplastes ceriferus, was synthesized by means of an intramolecular Ylttig-type reaction.
Thermal rearrangement and acid-catalyzed cyclization of all possible geometrical isomers of hedycaryol were investigated. From the stereochemistry of the products, the reacting conformations were deduced. While three (E,E-, E,Z- AND Z,E-) isomers reacted through the crossed conformations, Z,Z-isomer
Two 14-membered diterpenes, 3Z-cembrene A and cembrenene, isolated from a 1) 2) 3) 4) References and Notes M. Kodama, Y. Matsuki and S. lt8, Tetrahedron Letters 3065 (1975). -I
Stereoselective synthesis of cubitene (11, a novel diterp-ene isolated from defense secretion of termites, has been accomplished using an intramolecular reaction of a-sulfenyl carbanion vi th epoxide. Hydride reduction of the ketone 11 obtalned by Claisen rearrangement occurred in unexpectedly high