Reactions and Stereochemistry of Organometallic Compounds Related to Asymmetric Synthesis and Catalytic Activity

与不对称合成和催化活性相关的有机金属化合物的反应和立体化学

• 批准号: 0092222
• 负责人: John Faller
• 金额: $ 46.8万
• 依托单位: Yale University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2001
• 资助国家: 美国
• 起止时间: 2001-02-01 至 2004-01-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0092222&HistoricalAwards=false
• 关键词: Reactions; Stereochemistry; Organometallic; Compounds; Related

Dr. John W. Faller, Chemistry Department, Yale University, is supported by the Inorganic, Bioinorganic, and Organometallic Chemistry Program for studies related to asymmetric and regioselective synthesis and catalysis using metal complexes. New strategies will be developed for asymmetric synthesis based on the use of readily available racemic precatalysts treated with an inexpensive chiral poison. The poison selectively deactivates one enantiomer of the racemic mixture. The remaining active enantiomer is used to catalyze an asymmetric reaction. This general strategy has been demonstrated for asymmetric hydrogenations and Lewis acid-catalyzed Diels-Alder reactions. More effective poisons will be developed and will be applied to the preparation of chiral catalysts for a broad range of asymmetric reactions. Pseudo-enantiomeric complexes, which are composed of bimetallics containing different chiral ligands, will be explored. Hemilabile ligands will be used to control the stereochemistry in catalytic intermediates. The racemization of chiral 16 electron intermediates can potentially decrease the selectivity of asymmetric catalysts. This racemization process and methods of controlling it will also be studied. An object which is not the same as its mirror image (e.g. a left compared to a right handed glove) is said to be chiral. Many pharmaceutical and agricultural chemicals are chiral and often only one of the two mirror image molecules is effective. Since it is difficult to obtain a single mirror image, the production of such molecules is an important goal in contemporary chemistry. In this project new strategies toward solving the problem of "asymmetric synthesis" will be applied to a broad range of reactions and new, more economic preparations of important molecules will be developed. In addition to the chemical research, this project has the important objective of training young scientists in the areas of metal catalysis and asymmetric synthesis.

Dr. John W. Faller，耶鲁大学化学系，由无机，生物无机和有机化学计划支持，研究与使用金属络合物的不对称和区域选择性合成和催化有关的研究。新的策略将开发的基础上使用的不对称合成的外消旋预催化剂处理一种廉价的手性毒药。毒物选择性地使外消旋混合物的一种对映异构体失活。剩余的活性对映异构体用于催化不对称反应。这种一般策略已被证明为不对称氢化和刘易斯酸催化的Diels-Alder反应。将开发出更有效的毒物，并将其应用于制备用于广泛不对称反应的手性催化剂。 拟对映体配合物，这是由双金属含有不同的手性配体，将被探索。半不稳定配体将用于控制催化中间体中的立体化学。手性16电子中间体的外消旋会降低不对称催化剂的选择性。本文还将研究这种外消旋化过程及其控制方法。 与其镜像不相同的物体（例如左手手套与右手手套相比）被称为手性的。 许多药物和农业化学品是手性的，并且通常两个镜像分子中只有一个是有效的。由于很难获得单一的镜像，因此生产这样的分子是当代化学的一个重要目标。在这个项目中，解决“不对称合成”问题的新策略将应用于广泛的反应，并将开发新的，更经济的重要分子的制备。除了化学研究外，该项目的重要目标是培养金属催化和不对称合成领域的年轻科学家。