Development and mechanistic investigation of a highly efficient iridium(V) silyl complex for the reduction of tertiary amides to amines

被引：0
|
作者：
机构：
[1] Park, Sehoon
[2] Brookhart, Maurice
来源：
Brookhart, M. (mbrookhart@unc.edu) | 1600年 / American Chemical Society卷 / 134期
关键词：
The cationic Ir(III) acetone complex (POCOP)Ir(H)2(acetone) + (POCOP = 2,6-bis(di-tert-butylphosphinito)phenyl) was shown to catalyze the reduction of a variety of tertiary amides to amines using diethylsilane as reductant. Mechanistic studies established that a minor species generated in the reaction, the neutral silyl trihydride Ir(V) complex (POCOP)IrH3(SiEt2H), was the catalytically active species. High concentrations of this species could be conveniently generated by treatment of readily available (POCOP)IrHCl with tert-butoxide in the presence of Et2SiH2 under H2. Thus, using this mixture in the presence of a trialkylammonium salt, a wide array of tertiary amides, including extremely bulky substrates, are rapidly and quantitatively reduced to tertiary amines under mild conditions with low catalyst loading. A detailed mechanistic study has been carried out and intermediates identified. In brief, (POCOP)IrH3(SiEt2H) reduces the amide to the hemiaminal silyl ether that, in the presence of a trialkylammonium salt, is ionized to the iminium ion, which is then reduced to the tertiary amine by Et 2SiH2. Good functional group compatibility is demonstrated, and a high catalyst stability has provided turnover numbers as high as 10 000. © 2011 American Chemical Society;
D O I：
暂无
中图分类号：
学科分类号：
摘要：
Journal article (JA)
引用
收藏
相关论文
共 15 条
  • [1] Development and Mechanistic Investigation of a Highly Efficient Iridium(V) Silyl Complex for the Reduction of Tertiary Amides to Amines
    Park, Sehoon
    Brookhart, Maurice
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (01) : 640 - 653
  • [2] Efficient and Selective Hydrosilylation of Secondary and Tertiary Amides Catalyzed by an Iridium(III) Metallacycle: Development and Mechanistic Investigation
    Corre, Yann
    Trivelli, Xavier
    Capet, Frederic
    Djukic, Jean-Pierre
    Agbossou-Niedercorn, Francine
    Michon, Christophe
    CHEMCATCHEM, 2017, 9 (11) : 2009 - 2017
  • [3] Highly efficient low-valence tungsten-catalyzed deoxygenative reduction of tertiary amides to amines with pinacolborane
    Cheng, Biao
    Xv, Jialong
    Ren, Xiang
    Li, Yuanyuan
    Ji, Xiaoming
    Lu, Zhan
    ORGANIC CHEMISTRY FRONTIERS, 2025,
  • [4] Aluminium complex as an efficient catalyst for the chemo-selective reduction of amides to amines
    Das, Suman
    Karmakar, Himadri
    Bhattacharjee, Jayeeta
    Panda, Tarun K.
    DALTON TRANSACTIONS, 2019, 48 (31) : 11978 - 11984
  • [5] Diisobutylaluminum borohydride: An efficient reagent for the reduction of tertiary amides to the corresponding amines under ambient conditions
    Snelling, Rachel A.
    Amberchan, Gabriella
    Resendez, Angel
    Murphy, Chris L.
    Porter, Lauren
    Singaram, Bakthan
    TETRAHEDRON LETTERS, 2017, 58 (43) : 4073 - 4077
  • [6] NOVEL BORANE SELENIUM COMPLEX - HIGHLY SELECTIVE REDUCTION OF TERTIARY AMIDES AND NITRILES TO THE CORRESPONDING AMINES WITH SODIUM-BOROHYDRIDE DIALKYLSELENIUM DIBROMIDE
    AKABORI, S
    TAKANOHASHI, Y
    JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1991, (02): : 479 - 482
  • [7] Highly Efficient and Diastereoselective Gold(I)-Catalyzed Synthesis of Tertiary Amines from Secondary Amines and Alkynes: Substrate Scope and Mechanistic Insights
    Liu, Xin-Yuan
    Guo, Zhen
    Dong, Sijia S.
    Li, Xiao-Hua
    Che, Chi-Ming
    CHEMISTRY-A EUROPEAN JOURNAL, 2011, 17 (46) : 12932 - 12945
  • [8] A NOVEL HIGHLY SELECTIVE REDUCTION OF TERTIARY AMIDES TO AMINES WITH SODIUM BOROHYDRIDE-BIS(2-BROMOETHYL)SELENIUM DIBROMIDE
    AKABORI, S
    TAKANOHASHI, Y
    CHEMISTRY LETTERS, 1990, (02) : 251 - 252
  • [9] A Highly Efficient Mononuclear Iridium Complex Photocatalyst for CO2 Reduction under Visible Light
    Sato, Shunsuke
    Morikawa, Takeshi
    Kajino, Tsutomu
    Ishitani, Osamu
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2013, 52 (03) : 988 - 992
  • [10] Highly effective and hydrolytically stable vanadium(V) phenolato antitumor agents: development, analysis and mechanistic investigation
    Reytman, Lilia
    Tshuva, Edit Y.
    JOURNAL OF BIOLOGICAL INORGANIC CHEMISTRY, 2014, 19 : S795 - S796
12