Varseev Georgy N, Maier Martin E
Institut für Organische Chemie, Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, Germany.
Org Lett. 2007 Apr 12;9(8):1461-4. doi: 10.1021/ol070049a. Epub 2007 Mar 23.
[reaction: see text] The enantioselective total synthesis of (+)-neosymbioimine was accomplished in 18 steps from (-)-(S)-citronellol utilizing an organocatalytic alpha-oxidation of aldehyde 6. The carbon core was constructed by a tandem Horner-Wadsworth-Emmons (HWE) reaction and an intramolecular Diels-Alder cyclization. All double bonds of 12 were made in a stereoselective manner by Wittig-type reactions. Selective formation of the monosulfate monoester was accomplished by one-pot excessive sulfation followed by kinetic hydrolysis of bissulfate 18 in 79% yield.
[反应：见正文] 以（-）-（S）-香茅醇为原料，通过醛6的有机催化α-氧化反应，经18步完成了（+）-新共生亚胺的对映选择性全合成。碳骨架由串联的霍纳尔-沃兹沃思-埃蒙斯（HWE）反应和分子内狄尔斯-阿尔德环化反应构建而成。化合物12的所有双键通过维蒂希型反应以立体选择性方式构建。通过一锅法过量硫酸化，随后对硫酸氢盐18进行动力学水解，以79%的产率实现了单硫酸单酯的选择性形成。
