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亲核取代合成端炔2019-05-29

炔类化合物是有机合成中的重要中间体,目前已经发展出了一些非常常用的人名反应,例如Corey-Fuchs reaction, Seyferth-Gilbert reaction和 Sonogashira Coupling reaction。合成炔类化合物的方法按照反应类型可以分为两大类:官能团转化构建碳碳三键;在分子中引入带有碳碳三键的部分。但是在反合成设计上,按照炔基在分子中所处的位置(处于末端;或中间位置)对合成方法进行分类,更加方便应用,因此,接下来介绍的是末端炔烃的构建。

亲核取代合成端炔

端炔在碱的作用下,形成sp碳碳负离子,继而发生SN2反应,也是引入炔基的常用方法。

实例

To a flask was added 4.650 g (50.51 mmol,1.100 equiv) of lithium acetylide-ethylene diamine complex (commercially available) in 70.0 mL of DMSO. The suspension was stirred for several minutes, followed by the addition of 13.572 g (45.95 mmol) ofl-bromo-6-[(tert-butyldimethylsily1) oxylhexane (A) to the flask. The reaction mixture was stirred at 25 oC for 42 h, followed by the addition of 50 mL of water to the mixture. The mixture was extracted with three 100-mL portions of ether. The combined organic extracts were washed with one 100 mL portion of water and one 100 mL portion of a saturated brine solution and dried over anhydrous MgSO4, The extracts were filtered and the filtrate was concentrated in vacuo to yield orange/brown oil. Purification of the oil by distillation (78-80 oC, 0.85 mmHg) yielded 8.584 g (77.7%) of clear oil (P).

Reference: J. Org. Chem. 1991, 56, 2883–2894.

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