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Synthesis of Four Stereoisomers of ( S )‐2‐Methylpent‐3‐yl 3,13‐Dimethylpentadecanoate, a Sex Pheromone of the Bagworm Moth Clania variegate , Using Stereospecific Inversion of Secondary Sulfonates as a Key Step
Author(s) -
Taguri Tomonori,
Yamamoto Masanobu,
Fujii Toru,
Muraki Yuta,
Ando Tetsu
Publication year - 2013
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201300874
Subject(s) - chemistry , stereospecificity , moiety , enantiomer , enantioselective synthesis , racemization , sex pheromone , stereochemistry , organic chemistry , botany , biology , catalysis
Females of some lepidopteran species produce novel sex pheromones with a methyl‐branched structure, such as 2‐methylpent‐3‐yl 3,13‐dimethylpentadecanoate secreted by the bagworm moth Clania variegate . Recently, we have established a simple preparative method for the synthesis of methyl‐branched building blocks by utilizing an S N 2 reaction of chiral secondary tosylates derived from ( S )‐ and ( R )‐propylene oxides. The usefulness of these building blocks was demonstrated by their application in the synthesis of all four stereoisomers of an acid moiety in the bagworm pheromone. The enantiomeric purities of all building blocks were confirmed by enantioselective HPLC analysis. We found that a secondary mesylate was superior to the corresponding tosylate because it avoided an elimination side reaction, and racemization in the S N 2 reaction was not observed even at high temperature (150 °C). Finally, each optically active acid was esterified with ( S )‐2‐methyl‐3‐pentanol, which was synthesized by a new route starting from ( S )‐valine.