Russian Chemical Bulletin

, Volume 42, Issue 1, pp 98–99 | Cite as

Synthesis ofS-(+)-methoprene

  • V. N. Odinokov
  • G. Yu. Ishmuratov
  • R. Ya. Kharisov
  • E. P. Serebryakov
  • G. A. Tolstikov
Organic Chemistry

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.

Key words

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) 

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Copyright information

© Plenum Publishing Corporation 1993

Authors and Affiliations

  • V. N. Odinokov
    • 1
  • G. Yu. Ishmuratov
    • 1
  • R. Ya. Kharisov
    • 1
  • E. P. Serebryakov
    • 2
  • G. A. Tolstikov
    • 1
  1. 1.Institute of Organic Chemistry, the Ural BranchRussian Academy of SciencesUfaRussian Federation
  2. 2.N.D.Zelinsky Institute of Organic ChemistryRussian Academy of SciencesMoscowRussian Federation

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