Nitrogen transfer from a nitridomanganese(V) complex: Amination of silyl enol ethers
Nitrogen transfer from a nitridomanganese(V) complex: Amination of silyl enol ethers
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DOI：
10.1021/ja953659r
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发表时间：
1996-01-31
影响因子：
15
通讯作者：
Day, MW
中科院分区：
文献类型：
--
作者：
DuBois, J;Hong, J;Day, MW
金属催化的氧原子转移反应在化学和生物学中都具有根本意义。对生物系统中氧原子转移机制的详细研究导致了能够进行类似氧化化学的合成模型的产生。2这项工作推动了有价值的合成方法的发展，特别是关于烯烃环氧化，一个存在许多协议的反应。[3]相反，尽管相关的金属介导的氮原子转移反应技术在合成中得到了应用，但可用于该反应的方法较少。4，5在本文中，我们描述了两种新型氮化锰（V）salen衍生的络合物的制备，其可以被三氟乙酸酐（TFAA）活化用于氮转移。6，7当在某些甲硅烷基烯醇醚存在下进行该活化过程时，观察到N-三氟乙酰基R-氨基酮产物的快速形成（方程式1）。在氮原子转移化学的最早的实例之一中，格罗夫斯和Takahashi优雅地描述了使用氮并[内消旋-四（甲基）氨基]酮。（2，4，6-三甲基苯基）卟啉合]-锰（V），（TMPMnN），用于顺式-环辛烯的氮丙啶化。图8辐照对TMPMnN形成的影响
Metal-catalyzed oxygen atom-transfer reactions are of fundamental interest in both chemistry and biology. 1 Detailed investigations of the mechanism of oxygen atom transfer in biological systems have led to the generation of synthetic models capable of performing analogous oxidation chemistry. 2 This work has fueled the development of valuable synthetic methodology specifically with regard to alkene epoxidation, a reaction for which numerous protocols exist. 3 In contrast, fewer methods are available for the related metal-mediated nitrogen atom-transfer reaction, despite the utility of such technology in synthesis. 4, 5 Herein, we describe the preparation of two novel nitridomanganese (V) salen-derived complexes that can be activated for nitrogen transfer with trifluoroacetic anhydride (TFAA). 6, 7 When this activation process is conducted in the presence of certain silyl enol ethers, rapid formation of N-trifluoroacetyl R-amino ketone products is observed (eq 1).In one of the earliest examples of nitrogen atom-transfer chemistry, Groves and Takahashi elegantly described the use of nitrido [meso-tetrakis (2, 4, 6-trimethylphenyl) porphyrinato]-manganese (V),(TMPMnN), for the aziridination of cis-cyclooctene. 8 Formation of TMPMnN was effected by irradiation