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

10 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

Fingerprint

Lithium
Temperature

Keywords

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

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

Harnessing [1,4], [1,5], and [1,6] Anionic Fries-type Rearrangements by Reaction-Time Control in Flow. / Kim, Heejin; Inoue, Keita; Yoshida, Jun Ichi.

In: Angewandte Chemie - International Edition, Vol. 56, No. 27, 01.01.2017, p. 7863-7866.

Research output: Contribution to journalArticle

@article{49ad785ecca94b149fde48f399494b13,
title = "Harnessing [1,4], [1,5], and [1,6] Anionic Fries-type Rearrangements by Reaction-Time Control in Flow",
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.",
keywords = "aryllithium intermediates, flow chemistry, Fries rearrangement, microreactors, reactive intermediates",
author = "Heejin Kim and Keita Inoue and Yoshida, {Jun Ichi}",
year = "2017",
month = "1",
day = "1",
doi = "10.1002/anie.201704006",
language = "English",
volume = "56",
pages = "7863--7866",
journal = "Angewandte Chemie - International Edition",
issn = "1433-7851",
publisher = "John Wiley and Sons Ltd",
number = "27",

}

TY - JOUR

T1 - Harnessing [1,4], [1,5], and [1,6] Anionic Fries-type Rearrangements by Reaction-Time Control in Flow

AU - Kim, Heejin

AU - Inoue, Keita

AU - Yoshida, Jun Ichi

PY - 2017/1/1

Y1 - 2017/1/1

N2 - 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.

AB - 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.

KW - aryllithium intermediates

KW - flow chemistry

KW - Fries rearrangement

KW - microreactors

KW - reactive intermediates

UR - http://www.scopus.com/inward/record.url?scp=85020130364&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85020130364&partnerID=8YFLogxK

U2 - 10.1002/anie.201704006

DO - 10.1002/anie.201704006

M3 - Article

C2 - 28510344

AN - SCOPUS:85020130364

VL - 56

SP - 7863

EP - 7866

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

SN - 1433-7851

IS - 27

ER -