通过素催化级联异构化/无效化对Allenes进行灾难选择性合成
Yi Tang1, Wangyu Shi1, Juan Du1
1Department of Chemistry and Innovation Center of Pesticide Research, China Agricultural University, Beijing 100193, P. R. China.
一种新的素催化反应产生了具有五个奇拉中心的复杂基. 这种方法有效地合成了独特的六烯结构,并允许进一步转化为素替代化合物.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 合成方法论 合成方法论
背景情况:
- 艾伦系是有机合成中的多功能功能组.
- 复杂的多环基支架的立体选择性合成仍然是一个挑战.
- 级联反应为复杂的分子架构提供了高效的途径.
研究的目的:
- 开发一个在六水烯骨架上对烯的二选择性合成.
- 探索氨酸催化在级联异构化/取消反应中的实用性.
- 为了证明合成的艾伦的转化成其他有价值的化合物.
主要方法:
- 使用氨酸催化剂触发级联异构化和无效化序列.
- 采用一系列的酸和酸作为基板.
- 研究了立体化学结果,实现了高的二聚体选择性.
- 执行了艾伦产品的后续功能化.
主要成果:
- 成功合成了安装在包含五个奇拉中心和轴性奇拉性的六烯烯核心上的烯.
- 开发的反应表明了广泛的基质范围,耐受各种酸和酸.
- 烯产品被有效地转化为各种素替代的化环化合物.
结论:
- 一种新的素催化级联反应为复杂的阿伦提供了一条二分体选择性路径.
- 该方法使得能够构建功能密集的六胺烯骨架.
- 合成的艾伦基因作为进一步合成加工的有价值的中间体.
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相关概念视频
Preparation of Alkynes: Dehydrohalogenation
Alkynes can be prepared by dehydrohalogenation of vicinal or geminal dihalides in the presence of a strong base like sodium amide in liquid ammonia. The reaction proceeds with the loss of two equivalents of hydrogen halide (HX) via two successive E2 elimination reactions.
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
Preparation of Alkynes: Alkylation Reaction
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
