Emily B Corcoran1, Michael T Pirnot2, Shishi Lin3, Spencer D Dreher3, Daniel A DiRocco3, Ian W Davies3, Stephen L Buchwald4, David W C MacMillan5. 1. Merck Center for Catalysis at Princeton University, Princeton, NJ 08544, USA. 2. Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, USA. 3. Department of Process Chemistry, Merck Research Laboratories, Rahway, NJ 07065, USA. 4. Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, USA. dmacmill@princeton.edu sbuchwal@mit.edu. 5. Merck Center for Catalysis at Princeton University, Princeton, NJ 08544, USA. dmacmill@princeton.edu sbuchwal@mit.edu.
Abstract
Over the past two decades, there have been major developments in transition metal-catalyzed aminations of aryl halides to form anilines, a common structure found in drug agents, natural product isolates, and fine chemicals. Many of these approaches have enabled highly efficient and selective coupling through the design of specialized ligands, which facilitate reductive elimination from a destabilized metal center. We postulated that a general and complementary method for carbon-nitrogen bond formation could be developed through the destabilization of a metal amido complex via photoredox catalysis, thus providing an alternative approach to the use of structurally complex ligand systems. Here, we report the development of a distinct mechanistic paradigm for aryl amination using ligand-free nickel(II) salts, in which facile reductive elimination from the nickel metal center is induced via a photoredox-catalyzed electron-transfer event.
Over the past two decades, there have been major developments in transition metal-catalyzed aminations of n class="Chemical">aryl halides to form anilines, a common structure found in drug agents, natural product isolates, and fine chemicals. Many of these approaches have enabled highly efficient and selective coupling through the design of specialized ligands, which facilitate reductive elimination from a destabilized metal center. We postulated that a general and complementary method for carbon-nitrogen bond formation could be developed through the destabilization of a metal amido complex via photoredox catalysis, thus providing an alternative approach to the use of structurally complex ligand systems. Here, we report the development of a distinct mechanistic paradigm for aryl amination using ligand-free nickel(II) salts, in which facile reductive elimination from the nickelmetal center is induced via a photoredox-catalyzed electron-transfer event.
Authors: Zhiwei Zuo; Derek T Ahneman; Lingling Chu; Jack A Terrett; Abigail G Doyle; David W C MacMillan Journal: Science Date: 2014-06-05 Impact factor: 47.728
Authors: Russell T Smith; Xiaheng Zhang; Juan A Rincón; Javier Agejas; Carlos Mateos; Mario Barberis; Susana García-Cerrada; Oscar de Frutos; David W C MacMillan Journal: J Am Chem Soc Date: 2018-12-10 Impact factor: 15.419
Authors: Chao Li; Yu Kawamata; Hugh Nakamura; Julien C Vantourout; Zhiqing Liu; Qinglong Hou; Denghui Bao; Jeremy T Starr; Jinshan Chen; Ming Yan; Phil S Baran Journal: Angew Chem Int Ed Engl Date: 2017-09-14 Impact factor: 15.336
Authors: Rui Zhang; Guoqing Li; Michael Wismer; Petr Vachal; Steven L Colletti; Zhi-Cai Shi Journal: ACS Med Chem Lett Date: 2018-05-07 Impact factor: 4.345
Authors: Alex J Nett; Santiago Cañellas; Yuki Higuchi; Michael T Robo; Jeanne M Kochkodan; M Taylor Haynes; Jeff W Kampf; John Montgomery Journal: ACS Catal Date: 2018-06-11 Impact factor: 13.084