环状烯酰胺的Oxa-Diels-Alder反应构建手性氮氧螺杂环化合物

来源 :中国化学会第十六届全国有机合成化学学术研讨会 | 被引量 : 0次 | 上传用户:WPF0731
下载到本地 , 更方便阅读
声明 : 本文档内容版权归属内容提供方 , 如果您对本文有版权争议 , 可与客服联系进行内容授权或下架
论文部分内容阅读
  氮氧螺杂环骨架广泛存在于天然产物的核心结构中,具有独特的生物活性,如钙通道抑制活性(LycoplanineA),以及对多种肿瘤的抗增殖活性(青霉素A).Diels-Alder(DA)反应是构建六元环体系最重要和最基础的方式之一.目前为止,只有少数报道了对映体选择性反电子需求氧杂Diels-Alder反应,它们主要利用,α,β-不饱和羰基化合物作为双烯化合物与富电子烯烃进行环加成反应.1因此,研究其他不同类型底物的双烯体和亲二烯体的不对称反电子需求氧杂Diels-Alder反应具有重要的意义. 我们研究了环内含有碳氮双键官能团的不对称加成,发展合成cc位含有立体中心的手性氮杂环结构单元的方法.2环状烯酰胺既具有亲电性(α位碳原子),也具有亲核性(β位碳原子),作为底物引起我们的关注.邻羟基二苯甲醇通过酸催化脱水可得到邻醌甲基中间体(o-QMS),能与富电子亲双烯体发生反电子需求的Oxa-Diels-Alder反应.因此我们通过酸催化环状稀酰胺与邻羟基二苯甲醇发生Oxa-Diels-Alder反应构建手性氮氧螺杂环化合物.通过对反应历程的分析,第一步环状烯酰胺对o-QMs进行共轭加成得到环状亚胺中间体,第二步羟基对环内碳氮双键的加成得到氮氧螺杂环化合物,这两步反应均会产生相应的手性中心,且得到的产物中氮氧杂原子分别在两个环中.当以磷酸二苯酯催化可以得到一系列中等收率的消旋体产物,而通过手性磷酸催化剂(CPA)催化可以得到一系列高对应选择性的氮氧螺杂环化合物.
其他文献
In recent decades,fluorescent probes for the detection of metal ions and anions have emerged with the comforting features of high selectivity and sensitivity,cost effectiveness,no prior preprocessing
甲苯及其衍生物在通常的认知里是作为溶剂来使用,但这类化合物的直接C(sp3)-H功能化为有机骨架中引入苄基提供了一种简单经济的方法.1迄今为止这样一种高效便捷的途径在不对称催化领域鲜有报道.
BODIPY(4,4-difluoro-4-bora-3a,4a-diaza-s-indacene)dyes1 have been increasingly used for various different applications,including labelling reagents,chemosensors,therapeutic agents,energy transfer cass
Boron dipyrromethene(BODIPY) dyes1 are now being widelyapplied in diverse research fields.2The growing success of thesecompounds is closely associated with their excellent spectroscopicand photophysic
As we all know that appropriate levels of metal ions and anions play an indispensable role in the tissue structures and physiological responses in living organisms.1The fluorescent sensors have receiv
在过去的几十年里,配位超分子体系的研究得到了很大的发展,主要包括金属大环、多面体、笼状结构、索烃等,这些结构在催化、分子识别等领域被人们所广泛关注1.
The tetrahydrocarbazole architecture is a privileged heterocyclic ring system.It not only widely exists in various naturally occurring alkaloids and pharmacologically active compounds,but also is feat
Natural and synthetic congeners of carbazole comprise a large group of therapeutically useful agents in medicinal chemistry.Herein a series of novel isopropanol-bridged sulfonyl carbazoles as novel po
A series of Ofloxacin imidazole hybrids as potentially antimicrobial agents have been successfully synthesized via multistep reactions starting from commercial ethyl acetoacetate and triethylorthoform
Natural products play an important role for the development of most of the biologically active compounds due to the presence of enormous structure and chemical diversity which cannot be matched by any