Synthese optisch aktiver 2-Methyl- und 2-Äthyl-1, 6-dioxaspiro [4.4]-nonan- und -[4.5]decan-Pheromone aus einem gemeinsamen chiralen Vorläufer

✍ Scribed by Ernst Hungerbühler; Reto Naef; Daniel Wasmuth; Dieter Seebach; Hans-Rudolf Loosli; Adolf Wehrli

• Publisher: John Wiley and Sons
• Year: 1980
• Tongue: German
• Weight: 797 KB
• Volume: 63
• Category: Article
• ISSN: 0018-019X
• DOI: 10.1002/hlca.19800630724

✦ Synopsis

Synthesis of Optically Active 2‐Methyl‐ and 2‐Ethyl‐1, 6‐dioxaspiro [4.4]nonane‐ and ‐[4.5]decane Pheromones from a Common Chiral Precursor

The versatility of the bromoepoxide 6 as chiral building block, which is readily available in both enantiomeric forms from malic acid, and which has previously been used for a vermiculine synthesis, is further demonstrated by the preparation of the title compounds 1, 3, 4 and 5. Alkylation of 1,3‐dithiane, first with the 1‐ethoxyethyl‐protected ω‐chloroalcohols 8b or 9b and then with the (S)‐(−)‐bromoepoxide 6, followed by oxirane opening with Selectride or methyl Gilman‐reagent creates the desired carbon skeletons and functionality patterns 14–17, in overall yields of 60–80%. Acetal and thioacetal hydrolyses directly furnish the spiroacetal target structures 1 and 3–5 as 3:2‐diastereomeric mixtures; the E/Z‐epimers 3 are separated by preparative GC. (Fig.).