Rule of Five Cyclizations in and 5-Hexenyl Radicals and Photocyclizations of 1,5-Hexadienes: Effect of 4-Oxa Substitution

Title:
Rule of Five Cyclizations in and 5-Hexenyl Radicals and Photocyclizations of 1,5-Hexadienes: Effect of 4-Oxa Substitution
Authors:
Matlin, Albert; Brinton, Karen F.; Nivaggioli, Belinda Tsao
Abstract:
The effect of 4-oxa substitution on the regiochemistry and rate of 5-hexenyl radical cyclizations was investigated, as a potential model for [2 + 2] photocycloadditions of 2-acyl-4-oxa-1,5-hexadienes. Increasing the electron density in the alkene decreases the rate of cyclization in the 4-oxa-hexenyl radicals, relative to the all carbon analogs, but has little effect on the regioselectivity of the cyclization. The radical model does not reproduce the high degree of 1,6 closure, observed in the [2 + 2] photocycloadditions for 4-oxa-1,5-hexadiene 1a. However, the radical model does reinforce the interpretation that ground state conformational effects, engendered by substitution remote from the reacting centers have important rate consequences for cyclization reactions. Copyright © 2007 John Wiley & Sons, Ltd.
Citation:
Matlin, Albert, K. F. Brinton, and B. T. Nivaggioli. 2007. "Rule of Five Cyclizations in and 5-Hexenyl Radicals and Photocyclizations of 1,5-Hexadienes: Effect of 4-Oxa Substitution." Journal of Physical Organic Chemistry 20(2): 83-87.
Publisher:
Wiley
DATE ISSUED:
2007
Department:
Chemistry
Type:
article
PUBLISHED VERSION:
10.1002/poc.1120
PERMANENT LINK:
http://hdl.handle.net/11282/310296

Full metadata record

DC FieldValue Language
dc.contributor.authorMatlin, Alberten_US
dc.contributor.authorBrinton, Karen F.en_US
dc.contributor.authorNivaggioli, Belinda Tsaoen_US
dc.date.accessioned2013-12-23T16:29:53Z-
dc.date.available2013-12-23T16:29:53Z-
dc.date.issued2007en
dc.identifier.citationMatlin, Albert, K. F. Brinton, and B. T. Nivaggioli. 2007. "Rule of Five Cyclizations in and 5-Hexenyl Radicals and Photocyclizations of 1,5-Hexadienes: Effect of 4-Oxa Substitution." Journal of Physical Organic Chemistry 20(2): 83-87.en_US
dc.identifier.issn0894-3230en_US
dc.identifier.urihttp://hdl.handle.net/11282/310296-
dc.description.abstractThe effect of 4-oxa substitution on the regiochemistry and rate of 5-hexenyl radical cyclizations was investigated, as a potential model for [2 + 2] photocycloadditions of 2-acyl-4-oxa-1,5-hexadienes. Increasing the electron density in the alkene decreases the rate of cyclization in the 4-oxa-hexenyl radicals, relative to the all carbon analogs, but has little effect on the regioselectivity of the cyclization. The radical model does not reproduce the high degree of 1,6 closure, observed in the [2 + 2] photocycloadditions for 4-oxa-1,5-hexadiene 1a. However, the radical model does reinforce the interpretation that ground state conformational effects, engendered by substitution remote from the reacting centers have important rate consequences for cyclization reactions. Copyright © 2007 John Wiley & Sons, Ltd.en_US
dc.publisherWileyen_US
dc.identifier.doi10.1002/poc.1120-
dc.subject.departmentChemistryen_US
dc.titleRule of Five Cyclizations in and 5-Hexenyl Radicals and Photocyclizations of 1,5-Hexadienes: Effect of 4-Oxa Substitutionen_US
dc.typearticleen_US
dc.identifier.journalJournal of Physical Organic Chemistryen_US
dc.identifier.volume20en_US
dc.identifier.issue2en_US
dc.identifier.startpage83en_US
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