Harnessing [1,4], [1,5], and [1,6] Anionic Fries-type Rearrangements by Reaction-Time Control in Flow

Heejin Kim, Keita Inoue, Jun Ichi Yoshida

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

A series of anionic Fries-type rearrangements of carbamoyl-substituted aryllithium intermediates were controlled by using flow microreactor systems. For the [1,4] and [1,5] rearrangements, the aryllithium intermediate formed before carbamoyl migration and the lithium alkoxide formed after carbamoyl migration can be selectively subjected to subsequent reactions with electrophiles by precisely controlling the residence time and temperature (−25 to −50 °C). In contrast, the [1,6] rearrangement is rather slow even at −25 °C. The absence of crossover products indicates the intramolecular nature of the carbamoyl group migration.

Original languageEnglish
Pages (from-to)7863-7866
Number of pages4
JournalAngewandte Chemie - International Edition
Volume56
Issue number27
DOIs
Publication statusPublished - 2017 Jan 1
Externally publishedYes

Keywords

  • aryllithium intermediates
  • flow chemistry
  • Fries rearrangement
  • microreactors
  • reactive intermediates

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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