Ruthenium-Catalyzed Oxidative Cyanation of Tertiary Amines with Molecular Oxygen or Hydrogen Peroxide and Sodium Cyanide: sp3 C−H Bond Activation and Carbon−Carbon Bond Formatio

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• 作者：Shun-Ichi Murahashi ; Takahiro Nakae ; Hiroyuki Terai ; Naruyoshi Komiya
• 刊名：Journal of the American Chemical Society
• 出版年：2008
• 出版时间：August 20, 2008
• 年：2008
• 卷：130
• 期：33
• 页码：11005-11012
• 全文大小：303K
• 年卷期：v.130,no.33(August 20, 2008)
• ISSN：1520-5126

文摘

Ruthenium-catalyzed oxidative cyanation of tertiary amines with molecular oxygen in the presence of sodium cyanide and acetic acid gives the corresponding α-aminonitriles, which are highly useful intermediates for organic synthesis. The reaction is the first demonstration of direct sp³ C−H bond activation α to nitrogen followed by carbon−carbon bond formation under aerobic oxidation conditions. The catalytic oxidation seems to proceed by (i) α-C−H activation of tertiary amines by the ruthenium catalyst to give an iminium ion/ruthenium hydride intermediate, (ii) reaction with molecular oxygen to give an iminium ion/ruthenium hydroperoxide, (iii) reaction with HCN to give the α-aminonitrile product, H₂O₂, and Ru species, (iv) generation of oxoruthenium species from the reaction of Ru species with H₂O₂, and (v) reaction of oxoruthenium species with tertiary amines to give α-aminonitriles. On the basis of the last two pathways, a new type of ruthenium-catalyzed oxidative cyanation of tertiary amines with H₂O₂ to give α-aminonitriles was established. The α-aminonitriles thus obtained can be readily converted to α-amino acids, diamines, and various nitrogen-containing heterocyclic compounds.