The C-C bond activation and skeletal rearrangement of cycloalkanone imine-by Rh(I) catalysts
The C-C bond activation and skeletal rearrangement of cycloalkanone imine-by Rh(I) catalysts
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DOI：
10.1021/ja0033537
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发表时间：
2001-01-31
影响因子：
15
通讯作者：
Lim, SG
中科院分区：
文献类型：
--
作者：
Jun, CH;Lee, H;Lim, SG
均相催化剂活化碳-碳键是目前有机金属化学研究的热点。然而，过渡金属催化CC键均相活化的例子有：2-9，CC键的脱羧裂解，3，全烯丙醇的β-烷基消除，4，环碳酸盐的β-脱羧开环，5，叔环丁醇的环裂解，6，等等。特别是，为了利用环应变的释放，过渡金属催化剂对环烷酮的裂解仅限于环丙烯酮、环丁酮7、环丁酮8和环丁酮9等应变环酮。另一方面，大的非应变环烷酮的催化CC键断裂是罕见的。我们最近报道了一种新的催化CC键激活非约束酮类化合物。在本报告中，我们希望描述一种非张力环烷酮亚胺的开环及其骨架重排。的反应cycloalkanoketimine 1,准备从环烷酮和2-amino-3-picoline 11与天津石化(1000摩尔%基于1)进行的((C8H14) 2 rhcl) 2(3 3摩尔%基于1)和Cy3P(6摩尔%)产生的混合物ring-opened烯基酮4和7-tridecanone(5)水解后(eq 1)。十二烯基酮4,包括终端和内部烯烃,可以氢化13 1 atm Pd的H2 / C给饱和烷基酮6。最初，氯胺酮1中的CC键被3中的铑(I)切割，得到（亚氨基酰基）铑（III）金属环配合物7，然后通过β-氢消除作用产生铑（III）氢化8（方案1）。在烯烃2存在的情况下
The activation of the carbon-carbon bond by homogeneous catalysts is of current interest in organometallic chemistry. 1 However, a few examples of the homogeneous catalytic activation of the CC bond by transition metal have been reported: 2-9 the decarbonylative cleavage of the CC bond, 3 the β-alkyl elimination of the homoallyl alcohol, 4 the β-decarboxylative ring opening of cyclic carbonate, 5 the ring cleavage of tert-cyclobutanol, 6 and so on. Especially, ring-cleavages of cycloalkanones by transition metal catalyst have been limited to strained cyclic ketones such as cyclopropenone, 7 cyclobutenone, 8 and cyclobutanones9 to take advantage of the release of the ring strain. On the other hand, catalytic CC bond cleavages of large unstrained ring-sized cycloalkanones are rare. We recently reported on the new catalytic CC bond activation of unstrained ketone compounds. 10 In this report, we wish to describe the ring-opening of an unstrained cycloalkanone imine and its skeletal rearrangement. The reaction of cycloalkanoketimine 1, prepared from cycloalkanone and 2-amino-3-picoline, 11 with 1-hexene (2, 1000 mol% based on 1) was carried out in the presence of [(C8H14) 2RhCl] 2 (3, 3 mol% based on 1) and Cy3P (6 mol%) to yield a mixture of the ring-opened alkenyl ketones 4 and 7-tridecanone (5) after hydrolysis (eq 1). 12Alkenyl ketone 4, consisting of terminal and internal olefins, 13 can be hydrogenated by 1 atm of H2 on Pd/C to give saturated alkyl ketone 6. Initially, the CC bond in ketimine 1 is cleaved by rhodium (I) in 3 to give an (iminoacyl) rhodium (III) metallacyclic complex 7, followed by β-hydrogen elimination to effect rhodium (III) hydride 8 (Scheme 1). In the presence of 2, the olefin