Electrophilic amination of Cu(I) catalyzed phenylmagnesium bromide with N,O-bis(trimethylsilyl) hydroxylamine in THF:N-donor solvent. Control of C-N and C-O chemoselectivity

KAHYA N. D., EROĞLU F.

JOURNAL OF ORGANOMETALLIC CHEMISTRY, cilt.899, 2019 (SCI-Expanded) identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 899
  • Basım Tarihi: 2019
  • Doi Numarası: 10.1016/j.jorganchem.2019.120884
  • Dergi Adı: JOURNAL OF ORGANOMETALLIC CHEMISTRY
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Anahtar Kelimeler: Electrophilic amination, N, O-bis(trimethylsilyl)hydroxylamine, Aryl Grignard reagents, Arylamines, Atom-economy, C-N coupling, GRIGNARD-REAGENTS, ORGANOCUPRATE CLUSTERS, ORGANOZINC REAGENTS, ALPHA-AMINATION, ALKYL-HALIDES, COPPER, AMINES, MECHANISM, MAGNESIUM, ARYL
  • Ankara Üniversitesi Adresli: Evet

Özet

Reaction of PhMgBr with (Me3Si) HNO(SiMe3)[TMSHA] in the presence of CuI or CuCN catalysis (10-20 mol %) in THF:cosolvent (cosolvent = HMPA or TMEDA) at room temperature can provide an atom-economic and step-economic access for arylamine synthesis starting from aryl Grignard reagents. Chemoselectivity to yield C-N or C-O coupling can be controlled by changing reaction parameters. Cu(I) catalyzed reaction of PhMgBr in THF or in THF:HMPA (or TMEDA) affords both C-N and C-O coupling products, i.e. aniline and phenol (mol ratio >= 7:3), whereas uncatalyzed reaction of PhMgBr gives phenol. Mechanisms were proposed for the solvent dependence of chemoselectivity in the coupling of both uncatalyzed and Cu(I) catalyzed Grignard reagent with (TMS)HNO(TMS). (C) 2019 Elsevier B.V. All rights reserved.