洞察Shibasaki的Li3(THF) n(BINOLate) 3Ln复合体中的基质结合以及催化中的影响.
Alfred J Wooten1, Patrick J Carroll, Patrick J Walsh
1P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104-6323, USA.
这项研究描述了新型异金属易斯酸的特征,揭示了基质与类中心的结合如何影响不对称的催化. 研究结果表明,胺中心可能不会对双酸基质进行合,从而影响催化反应中的酶选择性.
科学领域:
- 有机金属化学 有机金属化学
- 不对称的催化剂.
- 兰化物化学 兰化物化学
背景情况:
- 异金属易斯酸,特别是Li3(THF) n(BINOLate) 3Ln,是具有高反选择性的强大的不对称催化剂.
- 催化剂-基质相互作用和操作的精确机制仍然不完全理解.
研究的目的:
- 为了隔离和结构性地描述新的异金属复合体.
- 通过溶液结合研究和NMR光谱学研究催化剂-基质相互作用.
- 阐明兰化物和中心在催化活性和选择性中的作用.
主要方法:
- 对Li3(THF) n(BINOLate) 3Ln和Li3(py) 5(BINOLate) 3Ln复合物的隔离和X射线结构特征.
- 使用易斯基基基质类似物 (循环赫森,DMF,皮里丁) 的溶液结合研究.
- 兰化物诱导转移 (LIS) NMR光谱学与偏磁性兰化物复合体.
- 3的结构和溶液研究 (DMEDA) 3 (BINOLATE) 3Ln复合物.
主要成果:
- 7和8坐标异金属复合体的结构特征,具有不同的配体 (THF,).
- 证明了基质类型的结合与溶液中的兰化物中心.
- 选择性地将N,N'-二甲基乙二胺 (DMEDA) 与中心结合,形成二聚体纯复合物.
- 使用DMEDA添加剂的催化不对称反应产生了与现有催化剂可比的酶选择活性.
结论:
- 假设Li3 ((THF) n ((BINOLate) 3Ln复合体中的兰坦化物中心不会对双酸盐基质进行合.
- 提出了一种解释Li3(THF) n(BINOLate) 3La催化剂高反选择性的机制.
- 突出了DMEDA添加物的潜力,作为有效的不对称催化剂.
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