通过双重C-H激活,通过甲基因与甲基胺的脱水 [4 + 2] 循环添加
Yoshiaki Nakao1, Eiji Morita, Hiroaki Idei
1Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan. yoshiakinakao@npc05.mbox.media.kyoto-u.ac.jp
研究人员开发了一种新的催化反应,其中具有1-arylalkyl组的formamides与alkynes反应. 这通过使两种C-H键功能化而产生高度替代的二皮里衍生物.
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:
- 甲胺是多功能有机化合物.
- C-H 键功能化是合成化学的一个关键领域.
- 循环加法反应对于形成循环结构至关重要.
研究的目的:
- 开发一种新的合成途径,以获得二皮里衍生物.
- 探索和醇基的合作催化.
- 为了研究形式胺中C-H键的双重功能.
主要方法:
- 使用/试基 (AlMe3) 合作催化.
- 使用脱的 [4 + 2] 循环添加反应.
- 反应1 - 亚里基替代形式胺与基.
主要成果:
- 实现了前所未有的高度替代的二皮里衍生物的合成.
- 在循环添加产品方面表现出良好的产量.
- 展示了胺基中C(sp2) -H和C(sp3) -H键的双重功能.
结论:
- 开发的方法提供了一个高效的途径,复杂的二二.
- /AlMe3合作催化使新的C-H激活和循环添加成为可能.
- 这种转换突出了在有机合成中形成胺的新反应模式.
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相关概念视频
Cycloaddition Reactions: Overview
Electrophilic Addition to Alkynes: Halogenation
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
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.
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
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.
Cycloaddition Reactions: MO Requirements for Thermal Activation
