Crepin, D.F.P., Harrity, J.P.A., Jiang, J. et al. (3 more authors) (2014) A Mechanistic Study of the Lewis Base-Directed Cycloaddition of 2-Pyrones and Alkynylboranes. Journal of the American Chemical Society, 136 (24). 8642 - 8653. ISSN 0002-7863
Abstract
Significant rate enhancements in the Diels–Alder reaction of alkynes and 2-pyrones bearing a Lewis basic group are observed when a combination of alkynyltrifluoroborates and BF3·OEt2 is used. This process generates functionalized aromatic compounds with complete regiocontrol. The observed rate enhancement was studied by density functional theory methods and appears to originate from coordination of the diene substrate to a mixture of alkynylborane intermediates, followed by a Lewis acid-mediated product equilibration step. Evidence for this mechanism is presented, as is the enhanced promotion of the cycloaddition via the use of alternative Lewis acid promoters.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2014 American Chemical Society. This is an author produced version of a paper subsequently published in Journal of the American Chemical Society. Uploaded in accordance with the publisher's self-archiving policy. |
Dates: |
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Institution: | The University of Sheffield |
Academic Units: | The University of Sheffield > Faculty of Science (Sheffield) > Department of Chemistry (Sheffield) |
Depositing User: | Symplectic Sheffield |
Date Deposited: | 01 Oct 2015 15:23 |
Last Modified: | 15 Nov 2015 23:02 |
Published Version: | http://dx.doi.org/10.1021/ja501805r |
Status: | Published |
Publisher: | American Chemical Society |
Refereed: | Yes |
Identification Number: | 10.1021/ja501805r |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:90396 |