Decoupling deprotonation from metalation

Thia-fries rearrangement

Alan M. Dyke, Duncan M. Gill, Jeremy N. Harvey, Alison J. Hester, Guy C. Lloyd-Jones, M. Paz Muñoz, Ian R. Shepperson

Research output: Contribution to journalArticle

49 Citations (Scopus)

Abstract

(Chemical Equation Presented) Label-enabled: Studies with 2H-, 18O-, and 34S-labeled aryl triflates show that lithium diisopropylamide-mediated thia-Fries rearrangement proceeds through an irreversible ortho deprotonation (see scheme; DIPA = diisopropylamine, LDA = lithium diisopropylamide). In contrast, ortho metalation results exclusively in the generation of a benzyne.

Original languageEnglish
Pages (from-to)5067-5070
Number of pages4
JournalAngewandte Chemie - International Edition
Volume47
Issue number27
Early online date16 Jun 2008
DOIs
Publication statusPublished - 23 Jun 2008
Externally publishedYes

Fingerprint

Deprotonation
Lithium
Labels
diisopropylamine

Cite this

Dyke, A. M., Gill, D. M., Harvey, J. N., Hester, A. J., Lloyd-Jones, G. C., Muñoz, M. P., & Shepperson, I. R. (2008). Decoupling deprotonation from metalation: Thia-fries rearrangement. Angewandte Chemie - International Edition, 47(27), 5067-5070. https://doi.org/10.1002/anie.200800750
Dyke, Alan M. ; Gill, Duncan M. ; Harvey, Jeremy N. ; Hester, Alison J. ; Lloyd-Jones, Guy C. ; Muñoz, M. Paz ; Shepperson, Ian R. / Decoupling deprotonation from metalation : Thia-fries rearrangement. In: Angewandte Chemie - International Edition. 2008 ; Vol. 47, No. 27. pp. 5067-5070.
@article{b0dc71ee2155483a8beaab1ae890b753,
title = "Decoupling deprotonation from metalation: Thia-fries rearrangement",
abstract = "(Chemical Equation Presented) Label-enabled: Studies with 2H-, 18O-, and 34S-labeled aryl triflates show that lithium diisopropylamide-mediated thia-Fries rearrangement proceeds through an irreversible ortho deprotonation (see scheme; DIPA = diisopropylamine, LDA = lithium diisopropylamide). In contrast, ortho metalation results exclusively in the generation of a benzyne.",
keywords = "Basicity, Metalation, Migration, Rearrangements, Superbases",
author = "Dyke, {Alan M.} and Gill, {Duncan M.} and Harvey, {Jeremy N.} and Hester, {Alison J.} and Lloyd-Jones, {Guy C.} and Mu{\~n}oz, {M. Paz} and Shepperson, {Ian R.}",
year = "2008",
month = "6",
day = "23",
doi = "10.1002/anie.200800750",
language = "English",
volume = "47",
pages = "5067--5070",
journal = "Angewandte Chemie - International Edition",
issn = "1433-7851",
publisher = "John Wiley and Sons Ltd",
number = "27",

}

Dyke, AM, Gill, DM, Harvey, JN, Hester, AJ, Lloyd-Jones, GC, Muñoz, MP & Shepperson, IR 2008, 'Decoupling deprotonation from metalation: Thia-fries rearrangement', Angewandte Chemie - International Edition, vol. 47, no. 27, pp. 5067-5070. https://doi.org/10.1002/anie.200800750

Decoupling deprotonation from metalation : Thia-fries rearrangement. / Dyke, Alan M.; Gill, Duncan M.; Harvey, Jeremy N.; Hester, Alison J.; Lloyd-Jones, Guy C.; Muñoz, M. Paz; Shepperson, Ian R.

In: Angewandte Chemie - International Edition, Vol. 47, No. 27, 23.06.2008, p. 5067-5070.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Decoupling deprotonation from metalation

T2 - Thia-fries rearrangement

AU - Dyke, Alan M.

AU - Gill, Duncan M.

AU - Harvey, Jeremy N.

AU - Hester, Alison J.

AU - Lloyd-Jones, Guy C.

AU - Muñoz, M. Paz

AU - Shepperson, Ian R.

PY - 2008/6/23

Y1 - 2008/6/23

N2 - (Chemical Equation Presented) Label-enabled: Studies with 2H-, 18O-, and 34S-labeled aryl triflates show that lithium diisopropylamide-mediated thia-Fries rearrangement proceeds through an irreversible ortho deprotonation (see scheme; DIPA = diisopropylamine, LDA = lithium diisopropylamide). In contrast, ortho metalation results exclusively in the generation of a benzyne.

AB - (Chemical Equation Presented) Label-enabled: Studies with 2H-, 18O-, and 34S-labeled aryl triflates show that lithium diisopropylamide-mediated thia-Fries rearrangement proceeds through an irreversible ortho deprotonation (see scheme; DIPA = diisopropylamine, LDA = lithium diisopropylamide). In contrast, ortho metalation results exclusively in the generation of a benzyne.

KW - Basicity

KW - Metalation

KW - Migration

KW - Rearrangements

KW - Superbases

UR - http://www.scopus.com/inward/record.url?scp=49849097111&partnerID=8YFLogxK

U2 - 10.1002/anie.200800750

DO - 10.1002/anie.200800750

M3 - Article

VL - 47

SP - 5067

EP - 5070

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

SN - 1433-7851

IS - 27

ER -