二环丙基乙炔与重氮甲烷的催化反应：合成紫薇烷[4]

IF 1.7 4区化学 Q3 CHEMISTRY, MULTIDISCIPLINARY

Russian Chemical Bulletin Pub Date : 2025-04-28 DOI:10.1007/s11172-025-4580-z

E. V. Shulishov, O. A. Pantyukh, E. D. Streltsova, L. G. Menchikov, Yu. V. Tomilov

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引用次数: 0

摘要

在铜化合物的存在下，二环丙基乙炔与过量的重氮甲烷反应，依次生成由多键环丙烷生成的二环丙基环丙烯，然后生成1,3-二环丙基双环[1.1.0]丁烷。后者在反应条件下部分异构化为2,3-二环丙基丁烷-1,3-二烯，而后者又进行进一步的环丙烷化。因此，当使用8 - 10倍过量的重氮甲烷时，形成1,1-低环丙烷系列的碳氢化合物1,1 ' -双环丙基双环丙烷（ivyane[4]）。在Pd(acac)2的存在下，二环丙基丁二烯的单环丙烷化很容易进行，而第二双键的环丙烷化只有在大量过量重氮甲烷的情况下才会发生。

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Catalytic reaction of dicyclopropylacetylene with diazomethane: synthesis of ivyane[4]

The reaction of dicyclopropylacetylene with excess diazomethane in the presence of copper compounds leads successively first to dicyclopropylcyclopropene resulting from multiple bond cyclopropanation and then to 1,3-dicyclopropylbicyclo[1.1.0]butane. The latter under the reaction conditions partially isomerizes to 2,3-dicyclopropylbuta-1,3-diene, which, in turn, undergoes further cyclopropanation. As a result, when an 8–10-fold excess of diazomethane is used, a hydrocarbon of the 1,1-oligocyclopropane series, 1,1′-dicyclopropylbicyclopropane (ivyane[4]), is formed. Monocyclopropanation of dicyclopropylbutadiene readily proceeds in the presence of Pd(acac)₂, whereas cyclopropanation of the second double bond occurs only with a large excess of diazomethane.

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来源期刊

Russian Chemical Bulletin 化学-化学综合

CiteScore

2.70

自引率

47.10%

发文量

257

审稿时长

3-8 weeks

期刊介绍： Publishing nearly 500 original articles a year, by leading Scientists from Russia and throughout the world, Russian Chemical Bulletin is a prominent international journal. The coverage of the journal spans practically all areas of fundamental chemical research and is presented in five sections: General and Inorganic Chemistry; Physical Chemistry; Organic Chemistry; Organometallic Chemistry; Chemistry of Natural Compounds and Bioorganic Chemistry.