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Catalytic asymmetric aziridination of α,β-unsaturated aldehydes

Catalytic asymmetric aziridination of α,β-unsaturated aldehydes
Catalytic asymmetric aziridination of α,β-unsaturated aldehydes
The development, scope, and application of the highly enantioselective organocatalytic aziridination of α,β-unsaturated aldehydes is presented. The aminocatalytic azirdination of α,β-unsaturated aldehydes enables the asymmetric formation of β-formyl aziridines with up to >19:1 d.r. and 99% ee. The aminocatalytic aziridination of α-monosubstituted enals gives access to terminal α-substituted-α-formyl aziridines in high yields and up to 99% ee. In the case of the organocatalytic aziridination of disubstituted α,β-unsaturated aldehydes, the transformations were highly diastereo- and enantioselective and give nearly enantiomerically pure β-formyl-functionalized aziridine products (99% ee). A highly enantioselective one-pot cascade sequence based on the combination of asymmetric amine and N-heterocyclic carbene catalysis (AHCC) is also disclosed. This one-pot three-component co-catalytic transformation between α,β-unsaturated aldehydes, hydroxylamine derivatives, and alcohols gives the corresponding N-tert-butoxycarbonyl and N-carbobenzyloxy-protected β-amino acid esters with ee values ranging from 92-99%. The mechanisms and stereochemistry of all these catalytic transformations are also discussed.
asymmetric catalysisaziridines, domino reactions, hydroxylamines, unsaturated aldehydes
0947-6539
7904-7917
Deiana, Luca
3eff57b4-a9f5-4c7f-a484-4dee1588e5de
Dziedzic, Pawel
f1a3d742-6349-4e42-82c5-98f005aab0f7
Zhao, Gui-Ling
106737c0-2aeb-4805-a8d7-496b1ce04322
Vesely, Jan
1853ff19-a906-4321-bd69-f7e434176fc3
Ibrahem, Ismail
3cbac9c1-431b-4a1f-8c41-92aa617254b0
Rios, Ramon
609bedf2-e886-4d62-a676-a32b6f8c1441
Sun, Junliang
eed23e16-8e61-4b15-bd55-7e3a560438b3
Córdova, Armando
d2a1239f-708d-4f9c-bf7c-c095e9a27cac
Deiana, Luca
3eff57b4-a9f5-4c7f-a484-4dee1588e5de
Dziedzic, Pawel
f1a3d742-6349-4e42-82c5-98f005aab0f7
Zhao, Gui-Ling
106737c0-2aeb-4805-a8d7-496b1ce04322
Vesely, Jan
1853ff19-a906-4321-bd69-f7e434176fc3
Ibrahem, Ismail
3cbac9c1-431b-4a1f-8c41-92aa617254b0
Rios, Ramon
609bedf2-e886-4d62-a676-a32b6f8c1441
Sun, Junliang
eed23e16-8e61-4b15-bd55-7e3a560438b3
Córdova, Armando
d2a1239f-708d-4f9c-bf7c-c095e9a27cac

Deiana, Luca, Dziedzic, Pawel, Zhao, Gui-Ling, Vesely, Jan, Ibrahem, Ismail, Rios, Ramon, Sun, Junliang and Córdova, Armando (2011) Catalytic asymmetric aziridination of α,β-unsaturated aldehydes. Chemistry - A European Journal, 17 (28), 7904-7917. (doi:10.1002/chem.201100042). (PMID:21611987)

Record type: Article

Abstract

The development, scope, and application of the highly enantioselective organocatalytic aziridination of α,β-unsaturated aldehydes is presented. The aminocatalytic azirdination of α,β-unsaturated aldehydes enables the asymmetric formation of β-formyl aziridines with up to >19:1 d.r. and 99% ee. The aminocatalytic aziridination of α-monosubstituted enals gives access to terminal α-substituted-α-formyl aziridines in high yields and up to 99% ee. In the case of the organocatalytic aziridination of disubstituted α,β-unsaturated aldehydes, the transformations were highly diastereo- and enantioselective and give nearly enantiomerically pure β-formyl-functionalized aziridine products (99% ee). A highly enantioselective one-pot cascade sequence based on the combination of asymmetric amine and N-heterocyclic carbene catalysis (AHCC) is also disclosed. This one-pot three-component co-catalytic transformation between α,β-unsaturated aldehydes, hydroxylamine derivatives, and alcohols gives the corresponding N-tert-butoxycarbonyl and N-carbobenzyloxy-protected β-amino acid esters with ee values ranging from 92-99%. The mechanisms and stereochemistry of all these catalytic transformations are also discussed.

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More information

e-pub ahead of print date: 24 May 2011
Published date: 4 July 2011
Keywords: asymmetric catalysisaziridines, domino reactions, hydroxylamines, unsaturated aldehydes
Organisations: Chemistry

Identifiers

Local EPrints ID: 347736
URI: http://eprints.soton.ac.uk/id/eprint/347736
ISSN: 0947-6539
PURE UUID: 699baa85-19e0-4b2f-9ebf-76a0809fcef5
ORCID for Ramon Rios: ORCID iD orcid.org/0000-0002-3843-8521

Catalogue record

Date deposited: 29 Jan 2013 14:00
Last modified: 17 Dec 2019 01:38

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Contributors

Author: Luca Deiana
Author: Pawel Dziedzic
Author: Gui-Ling Zhao
Author: Jan Vesely
Author: Ismail Ibrahem
Author: Ramon Rios ORCID iD
Author: Junliang Sun
Author: Armando Córdova

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