Saha Biswajit, Lin Mei-Huey, RajanBabu T V
Department of Chemistry, The Ohio State University, Columbus, OH 43210, USA.
J Org Chem. 2007 Nov 9;72(23):8648-55. doi: 10.1021/jo071076h. Epub 2007 Oct 12.
Halide or alkoxide free yttrium-salen complexes are excellent catalysts for the ring opening of epoxides mediated by TMSCN and TMSN3. Substrate to catalyst ratios up to 10000 have been realized in these potentially useful reactions, which can be run under solvent-free conditions. Even though the enantioselectivities for the TMSCN-mediated reaction remains modest (best 77% ee), these studies with a highly tunable ligand system may provide further impetus for work in this important area of catalysis. Even though attempts to isolate a Y-cyanide complex, which was detected by in situ IR spectroscopy, failed, a related dimeric hydroxide complex was isolated. A kinetic study using in situ IR spectroscopy did not provide conclusive data to assign an order with respect to Y in this reaction.
不含卤化物或醇盐的钇-双水杨醛缩乙二胺配合物是由三甲基氰硅烷（TMSCN）和叠氮三甲基硅烷（TMSN₃）介导的环氧化物开环反应的优良催化剂。在这些潜在有用的反应中，底物与催化剂的比例高达10000，且反应可在无溶剂条件下进行。尽管TMSCN介导反应的对映选择性仍然一般（最佳为77% ee），但这些对高度可调配体系统的研究可能会为这一重要催化领域的工作提供进一步的推动。尽管通过原位红外光谱检测到了Y-氰化物配合物，但分离该配合物的尝试失败了，不过分离出了一种相关的二聚体氢氧化物配合物。使用原位红外光谱进行的动力学研究未能提供确凿数据来确定该反应中Y的反应级数。
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