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Diastereoselective SmI2 mediated cascade radical cyclisations of methylenecyclopropane derivatives - syntheses of paeonilactone B and 6-epi-paeonilactone A

Diastereoselective SmI2 mediated cascade radical cyclisations of methylenecyclopropane derivatives - syntheses of paeonilactone B and 6-epi-paeonilactone A
Diastereoselective SmI2 mediated cascade radical cyclisations of methylenecyclopropane derivatives - syntheses of paeonilactone B and 6-epi-paeonilactone A
The SmI2 mediated cascade cyclisations of several methylenecyclopropyl ketones have been examined and found to proceed with high diastereoselectivity, which is critically dependent on the presence of HMPA in the reaction. In one case the radical species at the end of the cascade sequence underwent an unexpected and highly stereoselective dimerisation. The cascade methodology has been applied to a short synthesis of (+/-)-paeonilactone B and of (+/-)-6-epi-paeonilactone A.
divalent lanthanide derivatives, samarium(ii) iodide, organic-synthesis, stereoselective synthesis, cyclization reactions, acyclic precursors, r-(-)-carvone, dimerization, sequence, systems
0300-922X
487-496
Boffey, Raymond J.
939ca534-397e-4099-8ef7-968735337569
Whittingham, William G.
f84b39e9-7303-43ad-944e-26d5c8bc3969
Kilburn, Jeremy D.
e64ded70-825a-40ec-816b-c4605e007e7a
Boffey, Raymond J.
939ca534-397e-4099-8ef7-968735337569
Whittingham, William G.
f84b39e9-7303-43ad-944e-26d5c8bc3969
Kilburn, Jeremy D.
e64ded70-825a-40ec-816b-c4605e007e7a

Boffey, Raymond J., Whittingham, William G. and Kilburn, Jeremy D. (2001) Diastereoselective SmI2 mediated cascade radical cyclisations of methylenecyclopropane derivatives - syntheses of paeonilactone B and 6-epi-paeonilactone A. Journal of the Chemical Society, Perkin Transactions 1, (5), 487-496. (doi:10.1039/b009513n).

Record type: Article

Abstract

The SmI2 mediated cascade cyclisations of several methylenecyclopropyl ketones have been examined and found to proceed with high diastereoselectivity, which is critically dependent on the presence of HMPA in the reaction. In one case the radical species at the end of the cascade sequence underwent an unexpected and highly stereoselective dimerisation. The cascade methodology has been applied to a short synthesis of (+/-)-paeonilactone B and of (+/-)-6-epi-paeonilactone A.

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More information

Published date: 2001
Keywords: divalent lanthanide derivatives, samarium(ii) iodide, organic-synthesis, stereoselective synthesis, cyclization reactions, acyclic precursors, r-(-)-carvone, dimerization, sequence, systems

Identifiers

Local EPrints ID: 19414
URI: http://eprints.soton.ac.uk/id/eprint/19414
ISSN: 0300-922X
PURE UUID: 2e93f117-3f15-406c-9e95-0844aa222d73

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Date deposited: 14 Feb 2006
Last modified: 15 Mar 2024 06:15

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Contributors

Author: Raymond J. Boffey
Author: William G. Whittingham
Author: Jeremy D. Kilburn

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