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Kinetics of iminium ion catalysis

Kinetics of iminium ion catalysis
Kinetics of iminium ion catalysis
To a stirred solution of cinnamaldehyde (118 mg, 1.42 mmol, 122 ?l) in methanol (2ml), trifluoromethylpyrrolidine (198 mg, 1.42 mmol) was added and allowed to stir at ambient temperature for 2 minutes. After this time, hexafluorophosphoric solution in H2O (60% w/w) (345 mg, 1.42 mmol, 210 ?l) was added which immediately formed a yellow precipitate on addition. The excess solvent was removed in vacuo and the crude mixture was recrystallised from hot methanol to give 6 (493 mg, 87%) as an off white solid; mp 199-201 oC; ?max(Nujol) 2923, 2853, 1621, 1591, 1456, 1376 cm-1; 1H NMR (400MHz, CD3CN) ? 8.64 (d, J = 10.6 Hz, 1H), 8.12 (d, J = 15.2 Hz, 1H), 7.91-7.89 (m, 2H), 7.69-7.67 (m, 1H), 7.60-7.57 (m, 2H), 7.32 (dd, J = 10.6Hz, 15.2Hz, 1H), 5.0-4.96 (m, 1H), 4.24-4.14 (m, 2H), 2.52-2.45 (m, 1H), 2.42-2.27 (m, 3H); 13C NMR (125 MHz, CDCl3) ? 170.8, 165.3, 134.9, 131.2, 129.7, 125.1, 118.4, 66.8 (q, J1CF = 31.3 Hz), 53.3, 24.9, 22.6, 21.7; m/z (APCI) 254 [M–PF6]?+; HRMS (ES) found 254.1152 [M–PF6].+; calculated for C14H15NF3 254.1151.
organocatalysis, diels-alder reaction, beta-unsaturated aldehydes, transfer hydrogenation, enantioselective, 1, iminium ions, kinetics, organic catalysis, domino reactions, density functional calculations, organocatalytic conjugate addition, cycloaddition, alpha, metal-free, 3-dipolar cycloadditions, asymmetric
1433-7851
2820-2823
Evans, G.
e5f4d450-de59-4812-88d2-31033b6f5cce
Gibbs, T.J.K.
c7fd391c-9dcc-45a5-81d1-c80978fbe9a5
Jenkins, R.L.
87cc0911-447e-4bdc-b6cb-caa394894b2d
Coles, S.J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Hursthouse, M.B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Platts, J.A.
43d960e3-d149-4c7d-854b-3e5ac671bb05
Tomkinson, N.C.O.
b65328c2-f5e3-4061-8f5d-afb4fa8a9885
Evans, G.
e5f4d450-de59-4812-88d2-31033b6f5cce
Gibbs, T.J.K.
c7fd391c-9dcc-45a5-81d1-c80978fbe9a5
Jenkins, R.L.
87cc0911-447e-4bdc-b6cb-caa394894b2d
Coles, S.J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Hursthouse, M.B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Platts, J.A.
43d960e3-d149-4c7d-854b-3e5ac671bb05
Tomkinson, N.C.O.
b65328c2-f5e3-4061-8f5d-afb4fa8a9885

Evans, G., Gibbs, T.J.K., Jenkins, R.L., Coles, S.J., Hursthouse, M.B., Platts, J.A. and Tomkinson, N.C.O. (2008) Kinetics of iminium ion catalysis. Angewandte Chemie International Edition, 47 (15), 2820-2823. (doi:10.1002/anie.200705539).

Record type: Article

Abstract

To a stirred solution of cinnamaldehyde (118 mg, 1.42 mmol, 122 ?l) in methanol (2ml), trifluoromethylpyrrolidine (198 mg, 1.42 mmol) was added and allowed to stir at ambient temperature for 2 minutes. After this time, hexafluorophosphoric solution in H2O (60% w/w) (345 mg, 1.42 mmol, 210 ?l) was added which immediately formed a yellow precipitate on addition. The excess solvent was removed in vacuo and the crude mixture was recrystallised from hot methanol to give 6 (493 mg, 87%) as an off white solid; mp 199-201 oC; ?max(Nujol) 2923, 2853, 1621, 1591, 1456, 1376 cm-1; 1H NMR (400MHz, CD3CN) ? 8.64 (d, J = 10.6 Hz, 1H), 8.12 (d, J = 15.2 Hz, 1H), 7.91-7.89 (m, 2H), 7.69-7.67 (m, 1H), 7.60-7.57 (m, 2H), 7.32 (dd, J = 10.6Hz, 15.2Hz, 1H), 5.0-4.96 (m, 1H), 4.24-4.14 (m, 2H), 2.52-2.45 (m, 1H), 2.42-2.27 (m, 3H); 13C NMR (125 MHz, CDCl3) ? 170.8, 165.3, 134.9, 131.2, 129.7, 125.1, 118.4, 66.8 (q, J1CF = 31.3 Hz), 53.3, 24.9, 22.6, 21.7; m/z (APCI) 254 [M–PF6]?+; HRMS (ES) found 254.1152 [M–PF6].+; calculated for C14H15NF3 254.1151.

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More information

e-pub ahead of print date: 29 February 2008
Published date: 31 March 2008
Keywords: organocatalysis, diels-alder reaction, beta-unsaturated aldehydes, transfer hydrogenation, enantioselective, 1, iminium ions, kinetics, organic catalysis, domino reactions, density functional calculations, organocatalytic conjugate addition, cycloaddition, alpha, metal-free, 3-dipolar cycloadditions, asymmetric

Identifiers

Local EPrints ID: 54450
URI: http://eprints.soton.ac.uk/id/eprint/54450
ISSN: 1433-7851
PURE UUID: a485dc6d-4dd2-4ed6-b2e3-479da14ffc6a
ORCID for S.J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

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Date deposited: 06 Aug 2008
Last modified: 03 Dec 2019 01:55

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Contributors

Author: G. Evans
Author: T.J.K. Gibbs
Author: R.L. Jenkins
Author: S.J. Coles ORCID iD
Author: M.B. Hursthouse
Author: J.A. Platts
Author: N.C.O. Tomkinson

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