| 新型手性环状胺膦配体的设计合成及在酮的不对称还原中的应用 |
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| 引用本文： | 沈伟艺,余神銮,李岩云,高景星.新型手性环状胺膦配体的设计合成及在酮的不对称还原中的应用[J].中国科学:化学,2014(12):1893-1904. |
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| 作者姓名： | 沈伟艺 余神銮 李岩云 高景星 |
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| 作者单位： | 固体表面物理化学国家重点实验室;醇醚酯化工清洁生产国家工程实验室;厦门大学化学化工学院化学系; |
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| 基金项目： | 国家自然科学基金(21173176);教育部创新团队项目(IRT1036)资助 |
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| 摘 要： | 新型手性配体的设计合成是不对称催化研究的重要内容,其中手性胺膦配体因同时含有"软"的磷原子和"硬"的氮原子而具有丰富的配位化学性能和优秀的不对称诱导能力.本文总结了本研究组最近设计合成的手性环状胺膦配体的制备、表征及其在铁催化酮的不对称还原中的应用.手性1,2-环己二胺与双(2-甲酰基苯基)苯基膦通过2+2]环缩合反应能够顺利获得手性22元环的亚胺膦配体21,该配体经Na BH4还原后生成大环胺膦配体22.利用手性大环胺膦配体22与Fe3(CO)12原位生成的催化体系,能够高活性、高对映选择性地实现包括杂环芳香酮在内50多种酮的不对称转移氢化和不对称氢化反应,其S/C(底物与催化剂的摩尔比)最高可达5000:1,产物手性芳香醇的光学纯度高达99%ee.
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| 关 键 词： | 手性环状胺膦配体 不对称还原 不对称氢化 不对称转移氢化 芳香酮 |
Novel chiral macrocyclic ligands in asymmetric reduction of ketones |
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| SHEN WeiYi,YU ShenLuan,LI YanYun,GAO JingXing.Novel chiral macrocyclic ligands in asymmetric reduction of ketones[J].Scientia Sinica Chimica,2014(12):1893-1904. |
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| Authors: | SHEN WeiYi YU ShenLuan LI YanYun GAO JingXing |
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| Institution: | ( State Key Laboratory of Physical Chemistry of Solid Surfaces; National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters; Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China) |
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| Abstract: | The design and synthesis of novel chiral ligands plays an important role in asymmetric catalysis. In this feature article, we describe our recent studies of synthesis, characteration and application of novel chiral macrocyclic ligands. Novel chiral 22-membered macrocyclic ligands have been synthesized and the structures have been determined by an X-ray diffraction study. The catalytic systems in situ generated from the chiral macrocyclic ligand（R,R,R,R）-22 and the cheap, readily available Fe3（CO）12 exhibited high activity and excellent enantioselectivity with up to 99% ee in the asymmetric transfer hydrogenation as well as asymmetric hydrogenation of a wide variety of ketones. |
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| Keywords: | chiral macrocyclic animophosphine ligand asymmetric reduction asymmetric transfer hydrogenation asymmetric hydrogenation aromatic ketones |
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