Mild, Redox-Neutral Alkylation of !mines Enabled by an Organic Photocatalyst

被引:155
作者
Patel, Niki R. [1 ]
Kelly, Christopher B. [1 ]
Siegenfeld, Allison P. [1 ]
Molander, Gary A. [1 ]
机构
[1] Univ Penn, Roy & Diana Vagelos Labs, Dept Chem, 231 South 34th St, Philadelphia, PA 19104 USA
来源
ACS CATALYSIS | 2017年 / 7卷 / 03期
关键词
visible light; photocatalysis; imines; hypervalent silicon; radical alkylation; PHOTOREDOX/NICKEL DUAL CATALYSIS; SINGLE-ELECTRON TRANSMETALATION; RADICAL-ADDITION; NICKEL CATALYSIS; CARBON-CARBON; IMINES; LIGHT; SILICATES; ARYL; POLYMERIZATIONS;
D O I
10.1021/acscatal.6b03665
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
An operationally simple, mild, redox-neutral method for the photoredox alkylation of imines is reported. Utilizing an inexpensive organic photoredox catalyst, alkyl radicals are readily generated from the single-electron oxidation of ammonium alkyl bis(catecholato)silicates and are subsequently engaged in a C-C bond-forming reaction with imines. The process is highly selective, metal-free, and does not require a large excess of the alkylating reagent or the use of acidic additives.
引用
收藏
页码:1766 / 1770
页数:5
相关论文
共 41 条
  • [1] Quantification of the Electrophilic Reactivities of Aldehydes, Imines, and Enones
    Appel, Roland
    Mayr, Herbert
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2011, 133 (21) : 8240 - 8251
  • [2] Silicates as Latent Alkyl Radical Precursors: Visible-Light Photocatalytic Oxidation of Hypervalent Bis-Catecholato Silicon Compounds
    Corce, Vincent
    Chamoreau, Lise-Marie
    Derat, Etienne
    Goddard, Jean-Philippe
    Ollivier, Cyril
    Fensterbank, Louis
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2015, 54 (39) : 11414 - 11418
  • [3] Reductive Umpolung of Carbonyl Derivatives with Visible-Light Photoredox Catalysis: Direct Access to Vicinal Diamines and Amino Alcohols via α-Amino Radicals and Ketyl Radicals
    Fava, Eleonora
    Millet, Anthony
    Nakajima, Masaki
    Loescher, Sebastian
    Rueping, Magnus
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2016, 55 (23) : 6776 - 6779
  • [4] Synthesis of Enantiomerically Pure (α-Phenylalkyl)amines with Substituents at the ortho Position through Diastereoselective Radical Alkylation Reaction of Sulfinimines
    Fernandez-Salas, Jose A.
    Mercedes Rodriguez-Fernandez, M.
    Carmen Maestro, M.
    Garcia-Ruano, Jose L.
    [J]. EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2014, 2014 (24) : 5265 - 5272
  • [5] Intermolecular Alkyl Radical Additions to Enantiopure N-tert-Butanesulfinyl Aldimines
    Fernandez-Salas, Jose A.
    Carmen Maestro, M.
    Mercedes Rodriguez-Fernandez, M.
    Garcia-Ruano, Jose L.
    Alonso, Ines
    [J]. ORGANIC LETTERS, 2013, 15 (07) : 1658 - 1661
  • [6] Catalytic, asymmetric alkylation of imines
    Ferraris, Dana
    [J]. TETRAHEDRON, 2007, 63 (39) : 9581 - 9597
  • [7] The persistent radical effect: A principle for selective radical reactions and living radical polymerizations
    Fischer, H
    [J]. CHEMICAL REVIEWS, 2001, 101 (12) : 3581 - 3610
  • [8] Addition of carbon-centered radicals to imines and related compounds
    Friestad, GK
    [J]. TETRAHEDRON, 2001, 57 (26) : 5461 - 5496
  • [9] Scope of Stereoselective Mn-Mediated Radical Addition to Chiral Hydrazones and Application in a Formal Synthesis of Quinine
    Friestad, Gregory K.
    Ji, An
    Baltrusaitis, Jonas
    Korapala, Chandra Sekhar
    Qin, Jun
    [J]. JOURNAL OF ORGANIC CHEMISTRY, 2012, 77 (07) : 3159 - 3180