Systematic Synthesis of Terrestrial and Marine Terpenoid Dialdehydes

1.首次以7，8-二氢-β-亚氨基乙酸甲酯为原料，利用3-烯基-5-三甲基硅基呋喃的区域特异性单线态氧氧化生成-lt；β-gt；-烯基-lt；-γ&gt；-羟丁烯内酯的新方法，高产率地合成了甘露内酯和二甘露内酯。通过Pd(0)与α-硅基呋喃衍生物的催化偶联和还原反应，首次实现了以烯丙基氯为起始原料合成E-新构甲酰亚胺。以顺-1，2，3，6-四氢邻苯二甲酸酐为原料合成了多官能团环烯醚类化合物的关键中间体8，10-脱氢马钱素。以天然京尼平苷为原料，高效合成了具有光学活性的关键中间体。以关键中间体为原料，通过&lt；γ&gt；-羟基单环己烷的裂解反应，有效地合成了防腐菌素。用同样的方法合成了大环内酯类抗生素Brefeldin A。以京尼平为起始原料，合成了长春花素、二氢呋喃菊酯、尿囊素和白藜芦素。以芳香酮为原料合成了抗肿瘤倍半萜三环酸，并确定了三环酸和二次酮的绝对构型。

1. The first synthesis of manoalide and seco-manoalide from methyl 7,8-dihydro- <beta> -ionylidene acetate was achieved in high yield by the new method utilizing regiospecific singlet oxygen oxidation of 3-alkeny1-5-trimethylsilylfuran to <beta> -alkenyl- <gamma> -hydroxybutenolide. The first synthesis of E-neomanoalide from allylchloride was also achieved in short steps by Pd(0) catalized coupling with a <alpha> -silylfuran derivative and reduction.2. 8,10-dehydro-dehydrologanin, a key intermediate for the synthesis of poly-functional iridoids was synthesized from cis-1,2,3,6-tetrahydrophthalic anhydride. Optically active key intermediate was efficiently synthesized from natural geniposide. Secologanin was efficiently synthesized from key intermediate by the method involving fragmentation reaction of <gamma> -hydroxystannane. Brefeldin A, a macrolide antibiotics was also synthesized by the same method. Penstemide, didrovaltrate, allamandicin and plumericin were synthesized starting from genipin.3. Terrecyclic acid , antitumor sesquiterpene, was synthesized from (+)- fenchone and the absolute configuration of terrecyclic acid and quadrone was established.