Bruneau Christian, Renaud Jean-Luc, Demerseman Bernard
UMR 6226 CNRS-Université de Rennes 1, Sciences Chimiques de Rennes, Campus de Beaulieu-35042 Rennes Cedex, France.
Chemistry. 2006 Jul 5;12(20):5178-87. doi: 10.1002/chem.200600173.
Ruthenium(II) complexes containing the pentamethylcyclopentadienyl ligand efficiently perform the activation of allylic carbonates and halides to generate cationic and dicationic ruthenium(IV) complexes. This activation has been transferred as a key step to the catalytic allylation of nucleophiles. The structural and electronic properties of the allylic moieties lead to the regioselective formation of chiral products resulting from nucleophilic addition to their most substituted terminus. The catalytic activity of various Ru(Cp*) precatalysts in several allylic substitutions by C and O nucleophiles will be presented. The enantioselective version that has been demonstrated by using optically pure bisoxazoline ligands will also be discussed.
含有五甲基环戊二烯基配体的钌（II）配合物能有效地实现烯丙基碳酸酯和卤化物的活化，生成阳离子和二价阳离子钌（IV）配合物。这种活化作用已作为关键步骤转移到亲核试剂的催化烯丙基化反应中。烯丙基部分的结构和电子性质导致亲核加成到其取代最多的末端时，区域选择性地形成手性产物。将展示各种Ru（Cp*）预催化剂在几种由碳和氧亲核试剂进行的烯丙基取代反应中的催化活性。还将讨论使用光学纯双恶唑啉配体所证明的对映选择性反应。
