Stereoselective Synthesis of the Pheromone (R)-(–)-Sulcatol, and Its Enantiopure (R)- and (S)-1-Mono-, -1,1-Di-, and -1,1,1-Trifluoro Analogues[1]

✍ Scribed by Alberto Arnone; Pierfrancesco Bravo; Walter Panzeri; Fiorenza Viani; Matteo Zanda

• Publisher: John Wiley and Sons
• Year: 1999
• Tongue: English
• Weight: 285 KB
• Volume: 1999
• Category: Article
• ISSN: 1434-193X
• DOI: 10.1002/(sici)1099-0690(199901)1999:1<117::aid-ejoc117>3.0.co;2-i

✦ Synopsis

The pheromone (R)-(-)-sulcatol (10a) and three of its starting from chiral (R)-2-methyl-5-[(4-methylphenyl)sulfinyl]pent-2-ene (1) and commercially available fluorinated enantiomeric mono-, di-, and trifluoro analogues 10b-d have been synthesized, in six steps and with good overall yields, or non-fluorinated acetates.

Fluorination of organic compounds has been shown to cially available ethyl acetate and ethyl monofluoro-, difluoro-, and trifluoroacetates E, with the hexenyl p-tolyl sul-be particularly important in a number of fields, such as medicinal chemistry, bio-and agrochemistry, and material foxide D [10] to provide the key β-oxo sulfoxides C; 2) reduction of the β-oxo function of C to provide the β-hydroxy sciences. Fluorine alters considerably the physico-chemical properties of organic compounds, thus modifying the ac-sulfoxides B; 3) reductive desulfinylation of B, leading to the targeted sulcatol and 1-fluoro-substituted analogues A. tivity of biologically important molecules. [2] Fluoro-substituted molecules often have reduced melting points and are more volatile and hydrophobic: For these reasons, when considering the different classes of bioactive compounds, the preparation of fluoro-substituted insect hormones, sex pheromones and biosynthetic inhibitors is continually a subject of interest for insect pest control. [3] Population aggregation pheromones have been identified in several species of Scolytidae Coleoptera: [4] Sulcatol is the male-produced aggregation pheromone which was first isolated from the boring dust of Gnathotrichus Sulcatus, an economically important ambrosia beetle of the Pacific Coast of North Scheme 1. Retrosynthesis America. [5] Gnathotrichus Sulcatus is a timber pest which responds to this aggregation pheromone in a peculiar way