Taxane Diterpene Synthesis Studies. Part 2: Towards Taxinine—Enantiospecific Construction of an AB-ring Substructure Incorporating both Quaternary Carbon Centres and Attempts to Annulate the C-ring
作者:Martin G. Banwell、Malcolm D. McLeod、Andrew G. Riches
DOI:10.1071/ch03161
日期:——
In connection with efforts to develop an efficient total synthesis of the biologically active natural product taxinine 1, the enzymatically-derived and monochiral cis-1,2-dihydrocatechol 7 was converted, over several steps including a Diels–Alder cycloaddition reaction, into the bicyclo[2.2.2]octan-2-one 18. Reaction of the last compound with the organocerium reagent 22 afforded the 1,5-diene 23 which
在努力开发生物活性天然产物紫杉碱 1 的有效全合成过程中,酶促衍生的单手性 cis-1,2-二氢儿茶酚 7 经过几个步骤(包括 Diels-Alder 环加成反应)转化为双环[2.2.2]octan-2-one 18. 最后一个化合物与有机铈试剂22反应得到1,5-二烯23,其进行阴离子oxy-Cope重排反应,得到产物C-甲基化烯醇化物 25,双环 [5.3.1] 十一烯酮 27 体现了目标 1 的 AB 环系统。开发了两种用于此类产物的烯丙基氧化的方法,并且几次尝试进行环化反应以建立紫杉烷 C 环均未成功描述。