Macaulay Casper M, Ogawa Takahiko, McDonald Robert, Sydora Orson L, Stradiotto Mark, Turculet Laura
Department of Chemistry, Dalhousie University, 6274 Coburg Road, P.O. 15000, Halifax, Nova Scotia B3H 4R2, Canada.
Dalton Trans. 2019 Jul 2;48(26):9581-9587. doi: 10.1039/c8dt04221g.
A comparative study of the performance of (PN)M(N(SiMe3)2) (M = Mn, Fe, Co, and Ni) pre-catalysts supported by N-phosphinoamidinate ligation, as well as M(N(SiMe3)2)n (M = Li, Na, K, Mn, Fe, and Co) pre-catalysts, in the hydrosilative reduction of selected tertiary amide test substrates using PhSiH3 is reported. Encouraged by the performance observed herein for (PN)Ni(N(SiMe3)2) in the reduction of both N,N-dibenzylbenzamide and N,N-diisopropylbenzamide, further competitive testing involving the known complex (PN)Ni(NHdipp) (dipp = 2,6-diisopropylphenyl), as well as the new and crystallographically characterized mononuclear complexes (PN)Ni(OR) (R = 2,6-dimethylphenyl or tBu), revealed (PN)Ni(OtBu) to be particularly effective in such reduction chemistry, including transformations involving the secondary amides N-benzylbenzamide and caprolactam.
报道了由N-膦基亚胺配位支持的(PN)M(N(SiMe3)2)（M = Mn、Fe、Co和Ni）预催化剂以及M(N(SiMe3)2)n（M = Li、Na、K、Mn、Fe和Co）预催化剂在使用PhSiH3对选定的叔酰胺测试底物进行硅氢化还原反应中的性能比较研究。鉴于本文观察到(PN)Ni(N(SiMe3)2)在还原N,N-二苄基苯甲酰胺和N,N-二异丙基苯甲酰胺方面的性能，进一步的竞争性测试涉及已知配合物(PN)Ni(NHdipp)（dipp = 2,6-二异丙基苯基）以及新的且经晶体学表征的单核配合物(PN)Ni(OR)（R = 2,6-二甲基苯基或tBu），结果表明(PN)Ni(OtBu)在这种还原化学中特别有效，包括涉及仲酰胺N-苄基苯甲酰胺和己内酰胺的转化。
