Jin Jian, Chen Yile, Li Yannian, Wu Jinlong, Dai Wei-Min
Laboratory of Asymmetric Catalysis and Synthesis, Department of Chemistry, Zhejiang University, Hangzhou 310027, China.
Org Lett. 2007 Jun 21;9(13):2585-8. doi: 10.1021/ol0710360. Epub 2007 May 31.
Amphidinolide Y, a 17-membered cytotoxic macrolide isolated from marine dinoflagellates, has been synthesized via ring-closing metathesis to assemble the congested trisubstituted (E)-double bond. The seco precursor was prepared from readily available chiral synthons with the tetrahydrofuran ring formed via 5-endo epoxide ring-opening cyclization. It was found that the C6-keto seco substrate showed higher reactivity toward Grubbs' second generation catalyst while Schrock's Mo catalyst was completely inactive for formation of the macrocycle.
两性霉素Y是一种从海洋甲藻中分离得到的17元细胞毒性大环内酯类化合物，已通过闭环复分解反应合成，以构建拥挤的三取代（E）-双键。开链前体由容易获得的手性合成子制备，通过5-内型环氧化合物开环环化形成四氢呋喃环。研究发现，C6-酮基开链底物对格拉布第二代催化剂表现出更高的反应活性，而施罗克钼催化剂对大环的形成完全无活性。
