以炔为原料可调控合成碘代炔和二碘代烯烃
收稿日期: 2017-11-30
修回日期: 2018-01-08
网络出版日期: 2018-01-26
基金资助
国家自然科学基金（No.21502076）、合肥市百人计划、江西省杰出青年人才计划（No.20171BCB23039）资助项目.
Switchable Synthesis of Iodoalkynes and Diiodoalkenes from Terminal Alkynes
Received date: 2017-11-30
Revised date: 2018-01-08
Online published: 2018-01-26
Supported by
Project supported by the National Natural Science Foundation of China (No. 21502076), the Hundred-Talent Program of Hefei City and the Outstanding Young Talents Scheme of Jiangxi Province (No. 20171BCB23039).
碘代炔和二碘代烯烃作为有机中间体广泛地应用于C—C，C—O和C—N的构建反应中.因此，发展合成以上两类化合物的新方法具有一定的重要性.发展了一种新颖且可调控合成碘代炔和二碘代烯的方法.该方法使用端炔为原料，碘化锌和亚硝基叔丁酯为反应试剂.研究发现，在三乙胺的存在下该方法生成碘代炔，没有三乙胺的条件下生成二碘烯烃.以上合成碘代炔的方法具有操作简单、条件温和（弱碱和室温）和官能团兼容性好等特点.与之相比，二碘代烯烃对底物的电性有较严格的要求：只有负电性或者电中性的底物能发生反应.控制实验表明，碘代炔和二碘烯烃在包含最优条件的一系列反应条件下不能相互转化，控制实验结果可以由两个反应都经历了由碘代炔形成的碘鎓盐中间体来解释.
陈锁 , 章晓炜 , 赵辉 , 郭晓红 , 胡祥国 . 以炔为原料可调控合成碘代炔和二碘代烯烃[J]. 有机化学, 2018 , 38(5) : 1172 -1176 . DOI: 10.6023/cjoc201711050
Iodoalkynes and diiodoalkenes are valuable intermediates used extensively for C—C, C—O and C—N bonds formation. Therefore, the development of new method for the synthesis of these compunds is desirable. In this work, a novel and switchable protocol for the synthesis of iodoalkynes and diiodoalkenes has been developed, which were formed from terminal alkynes using the same reagent system of ZnI2 and tert-butyl nitrite in the presence or absence of triethylamine, respectively. The iodoalkyne formation is operationally simple, mild (weak base and room temperature), and tolerant of a large range of functional groups. In contrast, the diiodoalkene transformation shows interesting dependence on the electron property, and only electron-rich and neutral compounds are viable substrates. The control experiments performed suggest that iodoalkynes and diiodoalkenes are not interchangeable under a series of reaction conditions, including the optimized conditions, which can be explained by the mechanism in which both of the reactions involve a iodonium intermediate formed directly from a terminal alkyne.
Key words： iodoalkyne; diiodoalkene; tert-butyl nitrite; alkyne; zinc iodide
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