Organisch-Chemisches Institut der Universität Munster, Corrensstrasse 40, 48149 Münster, Germany.
J Am Chem Soc. 2009 Dec 16;131(49):17836-42. doi: 10.1021/ja905676a.
This study examined the reaction of in situ deprotonated acetonitrile with different chlorophosphines ClPR(2) (5a-d) to find new nitrile functionalized bis(diphenylphosphino)methane (dppm) ligands. Depending on the steric and electronic demand of the phosphines, very different and unexpected products (1b, 6, 9b and 11) were found. In the case of aryl-substituted phosphines (ClPPh(2) (5a) and ClPMes(2) (5b)), bis(diarylphosphino)acetonitrile compounds (1a and 1b) were found. Introduction of alkyl substituents at the ClPR(2) fragment (R = (t)butyl (5c) and cyclohexyl (5d)) changes the overall reaction behavior drastically. A new heteropentafulvene type structure (6), a P/N-disubstituted acetylene (9), and a P-substituted 3-amidocrotononitrile species (11) were found. Considering the experimental simplicity of these three-component reactions, these products are complex and their formations are highly organized. Most compounds were characterized by X-ray diffraction, NMR spectroscopy, and elemental analysis.
这项研究考察了原位脱质子的乙腈与不同氯膦(ClPR(2))（5a-d）的反应，以寻找新的腈官能化双(二苯基膦)甲烷(dppm)配体。根据膦的空间位阻和电子需求，得到了非常不同和出人意料的产物（1b、6、9b 和 11）。对于芳基取代的膦（ClPPh(2)（5a）和 ClPMes(2)（5b）），得到了双（二芳基膦）乙腈化合物（1a 和 1b）。在 ClPR(2)片段（R = (t)丁基（5c）和环己基（5d））上引入烷基取代基，会极大地改变整体反应行为。发现了一种新的杂戊二烯型结构（6）、一种 P/N-二取代乙炔（9）和一种 P-取代的 3-酰胺基丁腈类化合物（11）。考虑到这三种组分反应的实验简单性，这些产物非常复杂，其形成具有高度的组织性。大多数化合物通过 X 射线衍射、核磁共振波谱和元素分析进行了表征。
