Stereoselectivity in the complexing of platinum(II) chloride with substituted cyclopropanes
Stereoselectivity in the complexing of platinum(II) chloride with substituted cyclopropanes
复制标题
氯化铂(II)与取代环丙烷络合的立体选择性
DOI：
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发表时间：
1972
期刊：
影响因子：
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通讯作者：
K. G. Powell
中科院分区：
文献类型：
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作者：
F. J. Mcquillin;K. G. Powell
一系列单取代的环丙烷已被证明可以取代[（C2 H4）PtCl 2]2中的乙烯，形成取代的（丙烷-1，3-二基）PtCl 2衍生物，取代被吸电子取代基阻碍或抑制。从1H n.m.r.双吡啶衍生物（RC_3 H_5）PtCl_2（py）_2的光谱表明，当R = n-C_6 H_（13）、PhCH_2、o-NO_2C_6 H_4或Ph时，插入优先发生在取代度较低的环丙烷键上，而当R = p-MeC_6 H_4时，主要产物发生在取代度较高的环丙烷键上。反式-1，2-二苯基-和反式-1-甲基-2-正丁基-环丙烷经历PtCl 2插入到较少取代的环丙烷键中，但顺式-1-甲基-2-正丁基环丙烷和双环[4，1，0]庚烷优先异构化为烯烃。1，2-二环丙基乙烷产生双-PtCl 2衍生物。
A series of mono-substituted cyclopropanes have been shown to displace ethylene from [(C2H4)PtCl2]2 with formation of substituted (propane- 1,3-diyl)PtCl2 derivatives, displacement being impeded or inhibited by electron withdrawing substituents. From the 1H n.m.r. spectra of the bis-pyridine derivatives (RC3H5)PtCl2(py)2 it is shown that insertion occurs preferentially into the less substituted cyclopropane bond when R = n-C6H13, PhCH2, o-NO2C6H4, or Ph, but for R =p-MeC6H4 the principal product arises from insertion into the more substituted bond in the cyclopropane. trans-1,2-Diphenyl- and trans-1-methyl-2-n-butyl-cyclopropane undergo insertion of PtCl2 into the less substituted cyclopropane bond, but cis-1-methyl-2-n-butylcyclopropane and bicyclo[4,1,0]heptane are preferentially isomerised to olefins. 1,2-Dicyclopropylethane yields a bis-PtCl2 derivative.