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Chiral gold-catalyzed asymmetric reactions

Chiral gold-catalyzed asymmetric reactions. 报告人：刘槟. 2012 年 5 月 26 日. Diphosphine ligands controled Chiral gold(I) Catalysts. 1. 2. 3. (1). (2). 4. 5. Antonio M. Echavarren . Angew . Chem. Int. Ed . 2004 , 43, 2402 –2406. 6. (1). (2). (3). 7. 8. 9. 10.

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Chiral gold-catalyzed asymmetric reactions

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  1. Chiral gold-catalyzed asymmetric reactions 报告人：刘槟 2012年5月26日

  2. DiphosphineligandscontroledChiral gold(I) Catalysts 1.

  3. 2.

  4. 3. (1)

  5. (2)

  6. 4.

  7. 5.

  8. Antonio M. Echavarren. Angew. Chem. Int. Ed. 2004, 43, 2402 –2406

  9. 6. (1)

  10. (2) (3)

  11. 7.

  12. 8.

  13. 9.

  14. 10.

  15. MonophosphineligandscontroledChiral gold(I) Catalysts 1.

  16. 2. Similar work by F. Dean Toste using Phosphoramidite Gold(I) F. Dean Toste . J. Am. Chem. Soc. 2011, 133, 5500–5507

  17. 3.

  18. ChiralCarbenecontroledgold(I) Catalysts

  19. Chiral Anions controled gold(I) Catalysts

  20. Other Chiral Au(I)/Au(III) Catalysts

  21. Conclusion • 手性Au(I)催化的不对称反应最早可追溯到86年Ito与Hayashi的Adol反应，使用手性二茂铁膦配体。由于Au(I)配合物为线性配位模型，手性配体与催化剂活性位点距离较远，很难创造合适的手性环境。之后直至2005年手性金催化的反应才开始逐渐发展起来，目前主要的例子多集中于手性双膦配体的双金属催化剂。另外以手性Phosphoramidite为代表的单膦配体，手性卡宾配体以及由Toste提出的手性磷酸阴离子控制的手性Au(I)催化剂也有少数例子。 • 目前，手性金催化剂的发展还存在很多问题没有解决。例如，同其他金属相比金催化的反应多存在底物较窄的问题。手性双膦配体的双金属催化剂中第二个金属中心所起的作用并不明确。而手性单膦配体及手性卡宾金催化的例子较少且有一部分例子只能得到中等ee值。其他类型的手性配体也有待开发，如大位阻的手性硫脲类配体等等。

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