Phosphazene catalyzed addition to electron-deficient alkynes: the importance of non-linear allenyl intermediates upon stereoselectivity.

Journal article

Abstract:: An ONIOM QM/MM study on the mechanism of the Michael addition to triple bonds catalyzed by chiral diiminophosphorane catalysts has been performed to understand the stereoselectivity of the product olefin. Our results are consistent with the experimental enantioselectivity, but more importantly, reveal that the Z vs E preference depends on the influence of the catalyst upon the geometry of the allenyl enolate formed in the addition step. These intermediates show an innate preference for a (Z)-...
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Files:: Simon and Paton, Phosphazene catalyzed addition to electron-de...

(Preview, Accepted manuscript, pdf, 1.2MB, Terms of use)

Role:

Author

Institution:

University of Oxford

Oxford college:

St Hilda's College

Role:

Author

Language:: English
Keywords:: diiminophosphorane catalysts

Superbases

DFT calculations

Alkyne Addition

Organocatalysis

reaction mechanism

Phosphazene catalysts

Z/E selectivity
Pubs id:: pubs:686929
UUID:: uuid:784812e1-b4e5-4d0d-9472-a9b11ef0e93a
Local pid:: pubs:686929
Source identifiers:: 686929
Deposit date:: 2017-03-31

Copyright holder:: American Chemical Society
Notes:: Copyright © 2017 American Chemical Society. This is the accepted manuscript version of the article. The final version is available online from IOP Publishing at: http://dx.doi.org/10.1021/acs.joc.7b00540

Licence:: Terms and Conditions of Use for Oxford University Research Archive

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