Evidence for the Intermediacy of (η
<sup>3</sup>
‐Allyl)palladium Complexes in the Palladium‐Catalyzed Acryloxylation of Cycloalkenes: Unexpected Oxidation of 1,5‐Cyclooctadiene
作者:Sylvaine Jabre‐Truffert、Anne‐Marie Delmas、Helena Grennberg、Björn Akermark、Bernard Waegell
DOI:10.1002/(sici)1099-0690(200001)2000:1<219::aid-ejoc219>3.0.co;2-#
日期:2000.1
several cycloalkenes in the presence of the Pd(OAc)2/p-benzoquinone/MnO2 catalytic system is reported. This oxidation reaction yields allylic acrylates as the sole products through the intermediacy of an η3-allyl complex. However, with 1,5-cyclooctadiene (3), cyclooct-4-enone (4) is the major reaction product. Its formation results from oxidation, which is also observed in the palladium-catalyzed acetoxylation
报道了在Pd(OAc)2 /对-苯醌/ MnO 2催化体系存在下钯催化的几种环烯烃的丙烯氧化反应。该氧化反应通过的η的中间性产生烯丙基丙烯酸酯作为唯一的产物3 -烯丙基配合物。然而,对于1,5-环辛二烯(3),环辛-4-烯酮(4)是主要的反应产物。它的形成是由氧化引起的,在钯催化的3的乙酰氧基化反应中也观察到了这一点。已经表明,这是1,2-反式的结果加入(丙烯酰氧基palpalation),然后除去β-氢化物,得到烯醇丙烯酸酯或乙酸酯。在后者上进行第二次马尔可夫尼科夫定向的1,2-反丙烯氧基-钯合成钯配合物,其重排得到4。