Sterically facilitated meta-lithiation of arenes, containing electron-donating groups

Research output

Abstract

The influence of the bulky trimethylsilyl substituent on the selectivity of metallation of dimethylaniline, anisole and 1-dimethylaminonaphthalene is studied. The neighboring SiMe3 group forces dimethylamino and methoxy groups to occupy a conformation with an unshared electron pair turned towards silicon atom. This forced conformation prevents NMe2 and OMe groups from providing the DOM-effect, thus facilitating meta-metallation with the use of bulky LiCKOR. While the inverted NMe2 group completely suppresses ortho-metallation, the less bulky and more electron withdrawing OMe group demonstrates more rotation freedom allowing selective ortho-metallation with smaller reagents such as n-BuLi or tert-BuLi.

Original languageEnglish
Article number121068
JournalJournal of Organometallic Chemistry
Volume906
Early online date6 Dec 2019
DOIs
Publication statusPublished - 15 Jan 2020

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Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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