C-C bond-forming reactions of ground-state aryl halides under reductive activation

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

Under basic conditions aryl halides can undergo SRN1 reactions, BHAS reactions and benzyne formations. Appropriate complex substrates afford an opportunity to study inherent selectivities. SRN1 reactions are usually favoured under photoactivated conditions, but this paper reports their success using ground-state and transition metal-free conditions. In benzene, the enolate salt 12, derived by deprotonation of diketopiperazine 11, behaves as an electron donor, and assists the initiation of the reactions, but in DMSO, it is not required. The outcomes are compared and contrasted with a recent photochemical study on similar substrates. A particular difference is the prevalence of hydride shuttle reactions under relatively mild thermal conditions.
LanguageEnglish
Pages7875-7887
Number of pages13
JournalTetrahedron
Volume72
Issue number48
Early online date2 Jun 2016
DOIs
Publication statusPublished - 1 Dec 2016

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Diketopiperazines
Dimethyl Sulfoxide
Benzene
Ground state
Salts
Hot Temperature
Metals
Chemical activation
Electrons
Deprotonation
Substrates
Hydrides
Transition metals
benzyne

Keywords

  • radical
  • coupling
  • electron transfer
  • BHAS
  • SRN1
  • hydride shuttle reactions
  • benzyne formations

Cite this

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title = "C-C bond-forming reactions of ground-state aryl halides under reductive activation",
abstract = "Under basic conditions aryl halides can undergo SRN1 reactions, BHAS reactions and benzyne formations. Appropriate complex substrates afford an opportunity to study inherent selectivities. SRN1 reactions are usually favoured under photoactivated conditions, but this paper reports their success using ground-state and transition metal-free conditions. In benzene, the enolate salt 12, derived by deprotonation of diketopiperazine 11, behaves as an electron donor, and assists the initiation of the reactions, but in DMSO, it is not required. The outcomes are compared and contrasted with a recent photochemical study on similar substrates. A particular difference is the prevalence of hydride shuttle reactions under relatively mild thermal conditions.",
keywords = "radical, coupling, electron transfer, BHAS, SRN1, hydride shuttle reactions, benzyne formations",
author = "Emery, {Katie J.} and Tell Tuttle and Kennedy, {Alan R.} and Murphy, {John A.}",
year = "2016",
month = "12",
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doi = "10.1016/j.tet.2016.05.083",
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journal = "Tetrahedron",
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C-C bond-forming reactions of ground-state aryl halides under reductive activation. / Emery, Katie J.; Tuttle, Tell; Kennedy, Alan R.; Murphy, John A.

In: Tetrahedron, Vol. 72, No. 48, 01.12.2016, p. 7875-7887.

Research output: Contribution to journalArticle

TY - JOUR

T1 - C-C bond-forming reactions of ground-state aryl halides under reductive activation

AU - Emery, Katie J.

AU - Tuttle, Tell

AU - Kennedy, Alan R.

AU - Murphy, John A.

PY - 2016/12/1

Y1 - 2016/12/1

N2 - Under basic conditions aryl halides can undergo SRN1 reactions, BHAS reactions and benzyne formations. Appropriate complex substrates afford an opportunity to study inherent selectivities. SRN1 reactions are usually favoured under photoactivated conditions, but this paper reports their success using ground-state and transition metal-free conditions. In benzene, the enolate salt 12, derived by deprotonation of diketopiperazine 11, behaves as an electron donor, and assists the initiation of the reactions, but in DMSO, it is not required. The outcomes are compared and contrasted with a recent photochemical study on similar substrates. A particular difference is the prevalence of hydride shuttle reactions under relatively mild thermal conditions.

AB - Under basic conditions aryl halides can undergo SRN1 reactions, BHAS reactions and benzyne formations. Appropriate complex substrates afford an opportunity to study inherent selectivities. SRN1 reactions are usually favoured under photoactivated conditions, but this paper reports their success using ground-state and transition metal-free conditions. In benzene, the enolate salt 12, derived by deprotonation of diketopiperazine 11, behaves as an electron donor, and assists the initiation of the reactions, but in DMSO, it is not required. The outcomes are compared and contrasted with a recent photochemical study on similar substrates. A particular difference is the prevalence of hydride shuttle reactions under relatively mild thermal conditions.

KW - radical

KW - coupling

KW - electron transfer

KW - BHAS

KW - SRN1

KW - hydride shuttle reactions

KW - benzyne formations

UR - http://www.sciencedirect.com/science/article/pii/S0040402016305002

U2 - 10.1016/j.tet.2016.05.083

DO - 10.1016/j.tet.2016.05.083

M3 - Article

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SN - 0040-4020

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