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

doi:10.1002/anie.200800750

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 journal › Article › peer-review

70 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 language	English
Pages (from-to)	5067-5070
Number of pages	4
Journal	Angewandte Chemie - International Edition
Volume	47
Issue number	27
Early online date	16 Jun 2008
DOIs	https://doi.org/10.1002/anie.200800750
Publication status	Published - 23 Jun 2008
Externally published	Yes

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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",

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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

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JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 27

ER -

Decoupling deprotonation from metalation: Thia-fries rearrangement

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