| |
[摘要]：The diastereoselective synthesis of (S)-4-(2,2,4-trimethyl-1,3-dioxolan-4-yl)butan-1-ol, an intermediate in the asym. synthesis of the pine beetle pheromone (-)-frontalin [(1S,5R)-1,5-dimethyl-6,8-dioxabicyclo[3.2.1]octane], was accomplished starting from the b-keto sulfoxide, Me (SR)-6-[(4-methylphenyl)sulfinyl]-5-oxo-hexanoate (I), derived from glutaric anhydride. The key step of the synthetic sequence was the diastereoselective hydrocyanation of I by di-Et aluminum cyanide. The structure and abs. configuration of intermediates Me (5S)-6-amino-5-hydroxy-5-[(4-methylphenyl)sulfenylmethyl]-6-oxo-hexan oate [monoclinic, P21, a 11.457(1), b 5.4040(5), c 12.875(1) ? b 93.193(2)? V 795.9(1) ?, Z 2] and (2S)-2-hydroxy-2-[(4-methylphenyl)sulfenylmethyl]hexanedioic acid [monoclinic, P21, a 5.498(1), b 14.948(1), c 9.128(1) ? b 96.219(2)? V 745.8(2) ?, Z 2] were detd. by single crystal x-ray diffraction anal. |
|
