抗艾滋病天然产物biyouyanagin ab和到fuscins的全合成研究.docx

萄宵虫害 萄宵虫害 2DJo年兰j嗍大掌俘尘攀住论文 杜超 ④ 第二章：天然产物Biyouyanagin B和其他螺甾内酯相关天然产物的合成研究 对天然产物Biyouyanagin B进行合成研究以及结构的探索，同样以苯甲醛和乙酰乙酸 甲酯为原料，利用不对称烯丙基烷基化反应(Method C)，合成了4-epi．Hyperolactone C的 片段，并合成了天然产物Hyperolactone D和4-hydroxyHyperolactone D，并确定了 4-Hyperoxyhyperolactone D羟基的绝对构型。 分离文献中Biyouyanagin B结构确定不准确，对其结构进行探索研究。 用我们研究的方法对Hyperolactone A，Hyperolactone B进行合成研究。 第三章：Fuscin类抗艾滋病活性分子的合成研究 以苯乙酮没食子酸为原料，利用微波辅助的对位克莱森重排的关键反应，合成了关键 共同的中间体化合物(6)，双键重排，切断双键，以9步总产率33．4％首次合成了苯并二 氢吡喃型消旋天然产物Fuscinarin，用此中间体同时合成了苯并二氢吡喃型天然产物Fuscin 和Dihydrofuscin。 关键词：天然产物全合成·不对称烯丙基烷基化反应·抗HIV·相邻手性季碳· Biyouyanagin A．【2+2】光环化反应·Fuscin 蔫舛击亭 蔫舛击亭 2010年兰州大裳俘童掌侵伦文 杜超 露 Abstract This dissertation consiSted of three parts： Chapter l：Total synthesis ofAnti—HIV natural product Biyouyanagin A Using palladium-catalyzed asymmetric allylic alky’Iation as key reaction，we constructed two adjacent quaternary carbon centers with high enantioselectivity and diastereoselectivity．To improve the selectivity ofthe reaction，ligand(R R)一L2 Was used to instead of(R,R)．LI and the desired product WaS obtained with higher diastereoselectivity(26：1)and better enantioseleetivity (99％ee)，the ee value from 95％up to 99％，dr value increased from 8．7：1 to 26：1．This strategy has enabled the concise and efficient total syntheses of natural Hyperolactone C and (一)-Biyouyanagin A from benzaldehyde and methyl acetoacetate in only six and seven steps， respectively．The corresponding overall yields were 20％and 8％． The unnatural enantiomer ent-Hyperolactone C and(+)一Biyouyanagin A were also prepared by simply switching the chiral ligand in the Pd—AAA reaction and by changing the coupling partner in the final photoinduced【2+2】cycloaddition reaction． To extend research of asymmetric allylic alkylation on the substrate scope，the use of L2 as a 莓封虫害 莓封虫害 20Jo年兰删大学俘尘掌伍论文 杜超 ligand made ee values were all up to 99％and dr value ofup tO 56：1． Chapter 2：Study Oil the total synthesis of natural products Bi