Combining electronic and steric effects to generate hindered propargylic alcohols in high enantiomeric excess
Combining electronic and steric effects to generate hindered propargylic alcohols in high enantiomeric excess
Tethered ruthenium-TsDPEN complexes have been applied to the catalysis of the asymmetric transfer hydrogenation of a range of aryl/acetylenic ketones. The introduction of an ortho- substituent to the aryl ring of the substrate results in a reversal of the enantioselectivity, while the introduction of two o-fluoro substituents results in an improvement to the reduction enantioselectivity, as does the replacement of a phenyl ring on the alkyne with a trimethylsilyl group. These effects are rationalized as resulting from a change in the steric properties of the aryl ring and the electronic properties of the alkyne which, when matched in the reduction transition state, combine within a "window" of substrate/catalyst matching to generate products of high ee.
975-978
Vyas, Vijyesh K.
c8408d4e-852d-4dec-b85e-76f21ac121a4
Knighton, Richard C.
5a63128e-0ebd-466a-b327-3aee6e85a76d
Bhanage, Bhalchandra M.
6cbaae5e-22f3-4be5-b35e-129db35a82b5
Wills, Martin
4529569b-d977-463d-a99f-fccec46e21a0
3 January 2018
Vyas, Vijyesh K.
c8408d4e-852d-4dec-b85e-76f21ac121a4
Knighton, Richard C.
5a63128e-0ebd-466a-b327-3aee6e85a76d
Bhanage, Bhalchandra M.
6cbaae5e-22f3-4be5-b35e-129db35a82b5
Wills, Martin
4529569b-d977-463d-a99f-fccec46e21a0
Vyas, Vijyesh K., Knighton, Richard C., Bhanage, Bhalchandra M. and Wills, Martin
(2018)
Combining electronic and steric effects to generate hindered propargylic alcohols in high enantiomeric excess.
Organic Letters, 20 (4), .
(doi:10.1021/acs.orglett.7b03884).
Abstract
Tethered ruthenium-TsDPEN complexes have been applied to the catalysis of the asymmetric transfer hydrogenation of a range of aryl/acetylenic ketones. The introduction of an ortho- substituent to the aryl ring of the substrate results in a reversal of the enantioselectivity, while the introduction of two o-fluoro substituents results in an improvement to the reduction enantioselectivity, as does the replacement of a phenyl ring on the alkyne with a trimethylsilyl group. These effects are rationalized as resulting from a change in the steric properties of the aryl ring and the electronic properties of the alkyne which, when matched in the reduction transition state, combine within a "window" of substrate/catalyst matching to generate products of high ee.
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acs.orglett.7b03884
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Published date: 3 January 2018
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Local EPrints ID: 482093
URI: http://eprints.soton.ac.uk/id/eprint/482093
ISSN: 1523-7060
PURE UUID: 8dc7f6cf-817d-48e2-af2c-c4332ceb32e8
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Date deposited: 19 Sep 2023 16:34
Last modified: 18 Mar 2024 04:15
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Author:
Vijyesh K. Vyas
Author:
Richard C. Knighton
Author:
Bhalchandra M. Bhanage
Author:
Martin Wills
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