Synthesis of medium sized ring by radical ipso-substitution
Synthesis of medium sized ring by radical ipso-substitution
A new approach to seven, eight and nine membered ring synthesis involving a radical ipso-substitution is described. The method involves treatment of a 2-iodobenzyl-indanone or tetralone with tributyltin hydride and AIBN. Addition of the resulting aryl radical to the pendant carbocycle then occurred in a 5-exo-trig manner to the ring junction. Fragmentation of the resulting radical intermediate lead to rearomatisation of the arene and to the formation of a highly stabilised radical.
With tetralone derivatives the 5-exo-trig ipso-cyclisation completed with 6-endo/exo-ortho-addition while in the case of benzocyclobutane a competing 5-exo trig cyclisation to a nitrile was observed in addition to the formation of the seven membered ring.
A study on the use of tetrakistrimethylsilyl silane-TBAF for the reduction of the aryl halides is also presented.
University of Southampton
L'Hélias, Nathalie Sylvie
ae5ad565-bbc8-4385-bcff-e3ff1d4e92bb
2005
L'Hélias, Nathalie Sylvie
ae5ad565-bbc8-4385-bcff-e3ff1d4e92bb
L'Hélias, Nathalie Sylvie
(2005)
Synthesis of medium sized ring by radical ipso-substitution.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
A new approach to seven, eight and nine membered ring synthesis involving a radical ipso-substitution is described. The method involves treatment of a 2-iodobenzyl-indanone or tetralone with tributyltin hydride and AIBN. Addition of the resulting aryl radical to the pendant carbocycle then occurred in a 5-exo-trig manner to the ring junction. Fragmentation of the resulting radical intermediate lead to rearomatisation of the arene and to the formation of a highly stabilised radical.
With tetralone derivatives the 5-exo-trig ipso-cyclisation completed with 6-endo/exo-ortho-addition while in the case of benzocyclobutane a competing 5-exo trig cyclisation to a nitrile was observed in addition to the formation of the seven membered ring.
A study on the use of tetrakistrimethylsilyl silane-TBAF for the reduction of the aryl halides is also presented.
Text
968032.pdf
- Version of Record
More information
Published date: 2005
Identifiers
Local EPrints ID: 465500
URI: http://eprints.soton.ac.uk/id/eprint/465500
PURE UUID: 31bbaf95-e042-4b2a-9f46-8f5d7ad5481d
Catalogue record
Date deposited: 05 Jul 2022 01:28
Last modified: 16 Mar 2024 20:13
Export record
Contributors
Author:
Nathalie Sylvie L'Hélias
Download statistics
Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.
View more statistics