Radical Dearomatising Spirocyclisation of Benzisoxazole-Tethered Ynones

Nantachai Inprung; Adrian C. Whitwood; Richard J.K. Taylor; Michael J. James; William P. Unsworth

doi:10.1002/ejoc.202300603

Radical Dearomatising Spirocyclisation of Benzisoxazole-Tethered Ynones

Nantachai Inprung, Adrian C. Whitwood, Richard J.K. Taylor, Michael J. James^*, William P. Unsworth^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

The dearomative spirocyclisation of benzisoxazoles through a radical chain mechanism is described. Densely functionalised spirocycles were prepared in high yields by reacting benzisoxazole-tethered ynones with aryl thiols in 1,2-dichloroethane (DCE) at 60 °C. The identification of stabilising three-electron interactions was key to the development of this new radical cascade reaction. The obtained spirocyclic products were converted into other spirocyclic scaffolds through a two-step hydrogenolysis-cyclisation sequence.

Original language	English
Article number	e202300603
Journal	European Journal of Organic Chemistry
Early online date	27 Sept 2023
DOIs	https://doi.org/10.1002/ejoc.202300603
Publication status	E-pub ahead of print - 27 Sept 2023

Bibliographical note

Funding Information:
The authors would like to thank the Development and Promotion of Science and Technology Talents Project (DPST), Royal Thai Government. (N.I. EP/N035119/1), the University of York, and the University of Manchester for financial support. We would also like to thank Prof. Victor Chechik for helpful discussions.

Publisher Copyright:
© 2023 The Authors. European Journal of Organic Chemistry published by Wiley-VCH GmbH.

Keywords

cascade
dearomatisation
radical
ring expansion
spirocyclisation

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10.1002/ejoc.202300603Licence: CC BY

Eur J Org Chem - 2023 - Inprung - Radical Dearomatising Spirocyclisation of Benzisoxazole‐Tethered Ynones
© 2023 The Authors
Final published version, 2.95 MBLicence: CC BY

Cite this

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title = "Radical Dearomatising Spirocyclisation of Benzisoxazole-Tethered Ynones",

abstract = "The dearomative spirocyclisation of benzisoxazoles through a radical chain mechanism is described. Densely functionalised spirocycles were prepared in high yields by reacting benzisoxazole-tethered ynones with aryl thiols in 1,2-dichloroethane (DCE) at 60 °C. The identification of stabilising three-electron interactions was key to the development of this new radical cascade reaction. The obtained spirocyclic products were converted into other spirocyclic scaffolds through a two-step hydrogenolysis-cyclisation sequence.",

keywords = "cascade, dearomatisation, radical, ring expansion, spirocyclisation",

author = "Nantachai Inprung and Whitwood, {Adrian C.} and Taylor, {Richard J.K.} and James, {Michael J.} and Unsworth, {William P.}",

note = "Funding Information: The authors would like to thank the Development and Promotion of Science and Technology Talents Project (DPST), Royal Thai Government. (N.I. EP/N035119/1), the University of York, and the University of Manchester for financial support. We would also like to thank Prof. Victor Chechik for helpful discussions. Publisher Copyright: {\textcopyright} 2023 The Authors. European Journal of Organic Chemistry published by Wiley-VCH GmbH.",

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doi = "10.1002/ejoc.202300603",

language = "English",

journal = "European Journal of Organic Chemistry",

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T1 - Radical Dearomatising Spirocyclisation of Benzisoxazole-Tethered Ynones

AU - Inprung, Nantachai

AU - Whitwood, Adrian C.

AU - Taylor, Richard J.K.

AU - James, Michael J.

AU - Unsworth, William P.

N1 - Funding Information: The authors would like to thank the Development and Promotion of Science and Technology Talents Project (DPST), Royal Thai Government. (N.I. EP/N035119/1), the University of York, and the University of Manchester for financial support. We would also like to thank Prof. Victor Chechik for helpful discussions. Publisher Copyright: © 2023 The Authors. European Journal of Organic Chemistry published by Wiley-VCH GmbH.

PY - 2023/9/27

Y1 - 2023/9/27

N2 - The dearomative spirocyclisation of benzisoxazoles through a radical chain mechanism is described. Densely functionalised spirocycles were prepared in high yields by reacting benzisoxazole-tethered ynones with aryl thiols in 1,2-dichloroethane (DCE) at 60 °C. The identification of stabilising three-electron interactions was key to the development of this new radical cascade reaction. The obtained spirocyclic products were converted into other spirocyclic scaffolds through a two-step hydrogenolysis-cyclisation sequence.

AB - The dearomative spirocyclisation of benzisoxazoles through a radical chain mechanism is described. Densely functionalised spirocycles were prepared in high yields by reacting benzisoxazole-tethered ynones with aryl thiols in 1,2-dichloroethane (DCE) at 60 °C. The identification of stabilising three-electron interactions was key to the development of this new radical cascade reaction. The obtained spirocyclic products were converted into other spirocyclic scaffolds through a two-step hydrogenolysis-cyclisation sequence.

KW - cascade

KW - dearomatisation

KW - radical

KW - ring expansion

KW - spirocyclisation

UR - http://www.scopus.com/inward/record.url?scp=85172263828&partnerID=8YFLogxK

U2 - 10.1002/ejoc.202300603

DO - 10.1002/ejoc.202300603

M3 - Article

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SN - 1434-193X

JO - European Journal of Organic Chemistry

JF - European Journal of Organic Chemistry

M1 - e202300603

ER -

Radical Dearomatising Spirocyclisation of Benzisoxazole-Tethered Ynones

Abstract

Bibliographical note

Keywords

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