INTERMEDIATES FOR THE DEGENERATE AND PRODUCTIVE METATHESIS OF PROPENE ELUCIDATED BY THE METATHESIS REACTION OF (Z)-PROPENE-1-D1
INTERMEDIATES FOR THE DEGENERATE AND PRODUCTIVE METATHESIS OF PROPENE ELUCIDATED BY THE METATHESIS REACTION OF (Z)-PROPENE-1-D1
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DOI：
10.1021/ja00242a028
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发表时间：
1987-04-15
影响因子：
15
通讯作者：
MATSUMURA, C
中科院分区：
文献类型：
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作者：
TANAKA, K;TANAKA, K;MATSUMURA, C
用(Z)-丙烯-/-金属碳和金属环丁烷作为均相反应催化剂的中间体，确定了丙烯产化和简并反应的中间体。如果在非均相催化剂上的烯烃复分解反应是通过相同的中间体进行的，则丙烯的生产复分解应包括丙烯与亚甲基和乙炔的替代反应，如方案三所示。与产化反应同时发生的丙烯简并化反应也可能是由乙基或亚甲基中间体与丙烯反应引起的。那么一个有趣的问题就出现了：哪一种中间体对丙烯的简并复合体起主要作用？这是复分解反应中亚甲基交换烯烃的一个普遍问题。为了解决这一问题，Casey等人研究了(Z)-l-癸烯-/- Z /1与1-辛烷-l， l-d2在均相催化体系中的亚甲基交换反应，排除了这种可能性
Intermediates for productive and degenerate metathesis of propene were elucidated by using (Z)-propene-/-Metal carbene and metallacyclobutane have been accepted as intermediates in the homogeneous metathesis catalysts. 1 If olefin metathesis reaction on heterogeneous catalysts is occurring via the same intermediates, the productive metathesis of propene should involve alternative reaction of propene with methylidene and ethylidene as shown in Scheme III. The degenerate metathesis of propene which occurs simultaneously with the productive metathesis may also be caused by the reaction of either ethylidene or methylidene intermediate with propene. Then an interesting question arises: which intermediate contributes predominantly to the degenerate metathesis of propene? This is a general problem on methylene exchange of-olefm by the metathesis reaction. To solve this problem, Casey et al. studied the methylene-exchange reaction between (Z)-l-decene-/-z/1 and 1-octent-l, l-d2 in a homogeneous catalytic system, and they ruled out the possibility