| 任申勇,李连涛,张熠点,郭巧霞,申宝剑.化学通报,2021,84(10):1080-1085. |
| 用二茂锆配合物一锅法合成1,1’-二取代联烯 |
| One Pot Synthesis of 1,1’-Disubstituted Allenes Using Zirconocene Complexes |
| 投稿时间：2021-03-11 修订日期：2021-03-25 |
| DOI： |
| 中文关键词: 1,1’-二取代联烯 二氯二茂锆 1,4-二烷氧基-2-丁炔 锆杂环戊烯 烷氧基消除 |
| 英文关键词:1,1’-Disubstituted allene Zirconocene dichloride 1,4-Dialkoxy-2-butyne zirconacyclopentene Alkoxy elimination |
| 基金项目:中国石油大学(北京)科研基金项目(2462015YQ0313)资助 |
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| 中文摘要: |
| 二氯二茂锆（Cp2ZrCl2）与乙基溴化镁（EtMgBr）反应生成二乙基二茂锆（Cp2ZrEt2），再与1,4-二烷氧基-2-丁炔反应形成锆杂环戊烯，经过烷氧基在锆原子上的消除直接得到1,1’-二取代联烯（端联烯）。或者Cp2ZrCl2与正丁基锂（BuLi）反应生成二丁基二茂锆（Cp2ZrBu2），再与ɑ-烯烃反应形成锆杂环戊烷，然后与1,4-二烷氧基-2-丁炔反应形成锆杂环戊烯，经过烷氧基在锆原子上的消除得到端联烯。上述反应合成端联烯的收率都比较高，这为构造端联烯衍生物提供了一种简单实用的方法。 |
| 英文摘要: |
| The reaction of zirconocene dichloride (Cp2ZrCl2) with ethyl magnesium bromide (EtMgBr) afforded zirconocene diethyl (Cp2ZrEt2), which reacted with 1,4-dialkoxy-2-butyne to form zirconacyclopentene, after alkoxy group elimination on Zr 1,1’-disubstituted allene (terminal allene) derivative was obtained directly. Moreover the reaction of Cp2ZrCl2 with butyl lithium (BuLi) afforded zirconocenedibutyl (Cp2ZrBu2), which reacted with ɑ-olefin to form zirconacyclopentane, then with 1,4-dialkoxy-2-butyne to form zirconacyclopentene, after alkoxy group elimination on Zr terminal allene was also obtained directly. The reactions gave terminal allenes in good yields which provided a simple and useful method to construct terminal allene derivatives. |
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