用催化剂辅助的选择性乙化和四度碳中心的甲基乙化,使用tert-丁酸盐
Nirmala Mohanta1, Pragnya Paramita Samal2, Akanksha M Pandey1
1Department of Chemistry, Indian Institute of Science Education and Research, Pune, Maharashtra 411008, India.
这项研究引入了一种新的α-vinylation方法,使用 tert-butyl乙酸盐产生乙烯基组. 这种方法为合成乙烯基替代化合物提供了更安全,更容易获得的途径.
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:
- 四等碳中心是有机化学中重要的结构动图.
- 开发有效的方法来使这些中心发挥作用,对于合成复杂分子至关重要.
- 现有的α-vinylation方法通常涉及危险的试剂或有限的基质范围.
研究的目的:
- 介绍一种新的合成方法,用于氧功能化四元碳中心的α-化.
- 为了利用 tert-butyl乙酸作为安全和易于获得的 in situ 生成的 isobutylene 的来源.
- 探索选择性维尼化和甲基化化反应的催化系统.
主要方法:
- (III) 三叶酸[In(OTf) 3]催化α-乙烯基化反应.
- 在 ter-butyl乙酸中 in situ 生成异布烯.
- (II) 三叶酸 (Ni) 催化甲基化.
- 动力学研究和密度函数理论 (DFT) 计算.
主要成果:
- 使用 tert-butyl乙酸盐成功α-化氧功能化四级碳中心.
- 通过使用Ni(OTf) 2.2,表现出优异的甲基化对化的选择性.
- 合成的甲基烯基功能化1,4-氧-3-one衍生物来自过氧氧.
- 为观察到的选择性提供了机制性见解和合理化.
结论:
- 开发的In(OTf) 3催化反应为α-化提供了一条新且高效的途径.
- 特-乙酸乙酸作为一个实用和安全的先驱,用于乙烯基组的介绍.
- 催化剂的选择 (In(OTf) 3与Ni(OTf) 2) 决定了乙烯基和甲基化之间的选择性.
- 机理学研究阐明了反应途径和选择性决定因素.
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