Paramagnetic Palladacycles with PdIII Centers Are Highly Active Catalysts for Asymmetric Aza-Claisen Rearrangements

详细信息    查看全文

• 作者：Simon H. Eitel ; Matthias Bauer ; David Schweinfurth ; Naina Deibel ; Biprajit Sarkar ; Harald Kelm ; Hans-J枚rg Kr眉ger ; Wolfgang Frey ; Ren茅 Peters
• 刊名：The Journal of the American Chemical Society
• 出版年：2012
• 出版时间：March 14, 2012
• 年：2012
• 卷：134
• 期：10
• 页码：4683-4693
• 全文大小：619K
• 年卷期：v.134,no.10(March 14, 2012)
• ISSN：1520-5126

文摘

A combination of spectroscopic and electrochemical methods鈥擷ANES, EXAFS, X-ray, ¹H NMR, EPR, M枚ssbauer, and cyclic voltammetry鈥攄emonstrate that the most efficient Pd catalysts for the asymmetric rearrangement of allylic trifluoroacetimidates unexpectedly possess in the activated oxidized form a Pd^III center bound to a ferrocene core which remains unchanged (Fe^II) during the oxidative activation. These are the first recognized Pd^III complexes acting as enantioselective catalysts.