Download PDF
Synthesis 1992; 1992(1/2): 112-118
DOI: 10.1055/s-1992-34150
paper
© Georg Thieme Verlag, Rüdigerstr. 14, 70469 Stuttgart, Germany. All rights reserved. This journal, including all individual contributions and illustrations published therein, is legally protected by copyright for the duration of the copyright period. Any use, exploitation or commercialization outside the narrow limits set by copyright legislation, without the publisher's consent, is illegal and liable to criminal prosecution. This applies in particular to photostat reproduction, copying, cyclostyling, mimeographing or duplication of any kind, translating, preparation of microfilms, and electronic data processing and storage.

Directed ortho Metalation of O-Aryl and O-Pyridyl Thiocarbamates. A Versatile Synthetic Method for Substituted Phenol into Thiophenol Conversion

Francis Beaulieu* , Victor Snieckus
  • *Guelph-Waterloo Centre for Graduate Work in Chemistry University of Waterloo, Waterloo, Ontario N2L 3G1, Canada
Further Information

Publication History

Publication Date:
18 September 2002 (online)

  PDF Download  Permissions and Reprints All articles of this category

The preparation of ortho-substituted O-aryl and O-pyrid-3-yl thiocarbamates 7a-h and 11a-d and anionic ortho-Fries rearrangements of selected cases, [O-phenyl N,N-diethylthiocarbamate (6a) → N,N-diethyl-2-hydroxy-3-methylbenzenecarbothioamide (9), O-[4-(trimethylsilyl)pyridyl-3-yl] N,N-diethylthiocarbamate (11a) → N,N-diethyl-3-hydroxy-4-(trimethylsilyl)pyridine-3-carbothioamide (13)], via the directed ortho metalation protocol are described; coupled with their further thermal conversion (Kwart-Newman rearrangement) into S-thiocarbamate 8a-f and 12a-b and simple hydrolysis, this constitutes a new methodology for phenol to ortho-substituted thiophenol conversion (4 → 5).