1,3-Transposition of Allylic Alcohols Catalyzed by Methyltrioxorhenium

dc.contributor.author Jacob, Joseman
dc.contributor.author Espenson, James
dc.contributor.author Jensen, Jan
dc.contributor.author Gordon, Mark
dc.contributor.author Gordon, Mark
dc.contributor.department Ames Laboratory
dc.contributor.department Chemistry
dc.date 2018-02-17T07:50:12.000
dc.date.accessioned 2020-06-29T23:26:47Z
dc.date.available 2020-06-29T23:26:47Z
dc.date.copyright Thu Jan 01 00:00:00 UTC 1998
dc.date.issued 1998-04-01
dc.description.abstract <p>Methyltrioxorhenium (MTO) catalyzes the 1,3-transposition of allylic alcohols to generate the more stable isomer at equilibrium. The direction of the equilibrium is largely decided by the nature of the OH group, i.e., whether it is primary, secondary, or tertiary. In the case of aliphatic allylic alcohols, tertiary is preferred to secondary which is preferred to primary. For aromatic allyl alcohols, the more conjugated isomer predominates largely at equilibrium. Oxygen-18 labeling showed that the OH groups of the parent and product are the same. The reaction is first order with respect to both allyl alcohol and MTO but strongly inhibited by traces of water. Theoretical calculations suggest the same results in the case of aliphatic allyl alcohols, although aromatic allyl alcohols do not follow the predictions. Studies of deuterium-labeled substrates show a large <em>equilibrium</em> isotope effect (<em>K</em> = 1.20 ± 0.02). For isomeric allyl alcohols differing in the position of deuterium only, the isomer with the deuterium at the sp3center predominates at equilibrium. The effect of conjugation from a phenyl group appears to be less important since calculations suggest that the phenyl group is forced out of plane of the allylic π system.</p>
dc.description.comments <p>Reprinted (adapted) with permission from <em>Organometallics</em> 17 (1998): 1835, doi:<a href="http://dx.doi.org/10.1021/om971115n" target="_blank">10.1021/om971115n</a>. Copyright 1998 American Chemical Society.</p>
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dc.identifier archive/lib.dr.iastate.edu/ameslab_pubs/319/
dc.identifier.articleid 1321
dc.identifier.contextkey 7923221
dc.identifier.s3bucket isulib-bepress-aws-west
dc.identifier.submissionpath ameslab_pubs/319
dc.identifier.uri https://dr.lib.iastate.edu/handle/20.500.12876/7878
dc.language.iso en
dc.source.bitstream archive/lib.dr.iastate.edu/ameslab_pubs/319/0-L_1998_Gordon_TranspositionAllylic.pdf|||Fri Jan 14 23:32:55 UTC 2022
dc.source.bitstream archive/lib.dr.iastate.edu/ameslab_pubs/319/1998_Gordon_TranspositionAllylic.pdf|||Fri Jan 14 23:32:57 UTC 2022
dc.source.uri 10.1021/om971115n
dc.subject.disciplines Chemistry
dc.title 1,3-Transposition of Allylic Alcohols Catalyzed by Methyltrioxorhenium
dc.type article
dc.type.genre article
dspace.entity.type Publication
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relation.isOrgUnitOfPublication 42864f6e-7a3d-4be3-8b5a-0ae3c3830a11
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