ISSN:
1573-9171
Keywords:
S-(+)-methoprene, synthesis
;
S-(+)-3,7-dimethyl-1,6-octadiene, hydroalumination
;
6S,10-dimethyl-1,9-undecadien-4R/S-ol, Smidt oxygenation
;
isopropyl 3,7S,11-trimethyl-2E/Z,4E,10-dodecatrienoate, methoxylation at C(11)
Source:
Springer Online Journal Archives 1860-2000
Topics:
Chemistry and Pharmacology
Notes:
Abstract An optically active juvenile hormone analogue,S-(+)-methoprene (1), is synthesized in six steps from technical gradeS-(+)-3,7-dimethyl-1,6-octadiene (“(+)-dihydromyrcene”, e.e. −50%) by a novel procedure which begins with selective hydroalumination-oxidation to giveS-(-)-citronellol. This alcohol is oxidized to giveS-(-)-citronellal which on reaction with allylmagnesium chloride affords 6S, 10-dimethyl-1,9-undecadien-4 R/S-ol (5). Smidt-Moiseev oxygenation of 5 followed by dehydration leads to 6S, 10-dimethyl-3E,9-undecadien-2-one. The latter on treatment with isopropoxyethynylmagnesium bromide is transformed into isopropyl 3,7S,11-trimethyl-2E/Z,4,E,10-dodecatrienoate which upon Brown solvomercurationreduction in MeOH gives1 in 14% overall yield.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF00699984
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