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Synthesis 2000; 2000(13): 1863-1867
DOI: 10.1055/s-2000-8221
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Pheromones of Pine Sawflies: Synthesis of a Pure (2S,3R)-3-Methylalkan-2-ol Stereoisomer via an Asymmetric 1,3-Dipolar Cycloaddition; Preparation of a Pheromone Component of Macrodiprion nemoralis

Staffan Karlsson* , Hans-Erik Högberg
  • *Department of Chemistry and Process Technology, Mid Sweden University, SE-851 70 Sundsvall, Sweden; Fax + 46(60)14 88 02; E-mail: Staffan.Karlsson@kep.mh.se
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Publication Date:
31 December 2000 (online)

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This paper presents a new approach to the preparation of enantiomerically pure (2S,3R)-3-methylalkan-2-ols, the esters of which are sex pheromones of several pine sawflies. Thus, an asymmetric 1,3-dipolar cycloaddition between a sulfur containing 1,3-dipole and a dipolarophile attached to (1R)-camphorsultam containing a vinyl ether functionality furnished a 90 : 10 diastereomeric mixture of trans-3,4-disubstituted tetrahydrothiophene amides. The major one was converted to an enantiomerically pure tetrahydrothienylmethyl bromide, which was coupled with a monoalkylated dithiane unit. After Raney nickel reduction (2S,3R,7R,9S)-3,7,9-trimethyltridecan-2-ol was obtained, the acetate of which is the attractant sex pheromone component of Macrodiprion nemoralis. Because this new approach is quite efficient it can be valuable for the synthesis of similar compounds.

1,3-dipolar cycloaddition - asymmetric synthesis - pine sawflies - dithiane - Raney nickel - lithiations - desulfurisations