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Relative kinetic ordering of [1,3]-hydrogen migration, anionic oxy-cope rearrangement, and base-accelerated dehydration in tertiary cyclononatrienyl alkoxides

✍ Scribed by Gary D. Crouse; Leo A. Paquette


Book ID
104234186
Publisher
Elsevier Science
Year
1981
Tongue
French
Weight
264 KB
Volume
22
Category
Article
ISSN
0040-4039

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✦ Synopsis


The reactivity exhibited by l-methyl-and l-ethyl-cis3 -2,4,7-cyclononatrienol toward -KH under various conditions has been examined. Recent research activities have demonstrated that a highly ionized alkoxide substituent can substantially accelerate oxy-Cope rearrangements,i [1,51-dienyl hydrogen shifts,2 [1,33-? and [4+2] cycloreversions. 4 sigmatropic carbon migrations, At least where oxy-Cope rearrangements are concerned, excellent stereochemical control can be achieved, and stereoselective syntheses based on this principle have been described for (+)-juvabione,i the primary prostaglandins,2 various germacrane sesquiterpenes, 5 and (&)-coronafacic acid.6 Pivotal to our earlier