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One-pot organocatalytic domino Michael/alpha-alkylation reactions: direct catalytic enantioselective cyclopropanation and cyclopentanation reactions

One-pot organocatalytic domino Michael/alpha-alkylation reactions: direct catalytic enantioselective cyclopropanation and cyclopentanation reactions
One-pot organocatalytic domino Michael/alpha-alkylation reactions: direct catalytic enantioselective cyclopropanation and cyclopentanation reactions
The development of one-pot organocatalytic domino Michael/alpha-alkylation reactions between bromomalonates or bromoacetoacetate esters and alpha,beta-unsaturated aldehydes is presented. The chiral-amine-catalyzed reactions with bromomalonates as substrates give access to the corresponding 2-formylcyclopropane derivatives in high yields with excellent diastereoselectivity and up to 99 % ee. The catalytic domino Michael/alpha-alkylation reactions between 4-bromo-acetoacetate and enals provide a route for the synthesis of functionalized cyclopentanones in good to high yields with 93-99 % ee. The products from the organocatalytic reactions were also reduced with high diastereoselectivity to the corresponding cyclopropanols and cyclopentanols, respectively. Moreover, one-pot combinations of amine and heterocyclic carbene catalysis (AHCC) enabled the highly enantioselective synthesis of beta-malonate esters (91-97 % ee) from the reaction between bromomalonates and enals. The tandem catalysis included the catalytic domino reaction followed by catalytic in situ chemoselective ring-opening of the 2-formylcyclopropane intermediates.
unsaturated aldehydes, asymmetric catalysis, cyclopentanes, cyclopropanes, domino reactions, organocatalysis
0947-6539
7867-7879
Ibrahem, Ismail
3cbac9c1-431b-4a1f-8c41-92aa617254b0
Zhao, Gui-Ling
106737c0-2aeb-4805-a8d7-496b1ce04322
Rios, Ramon
609bedf2-e886-4d62-a676-a32b6f8c1441
Vesely, Jan
1853ff19-a906-4321-bd69-f7e434176fc3
Sundén, Henrik
fe114b08-1de1-4e88-9778-a9cddf3aa76d
Dziedzic, Pawel
f1a3d742-6349-4e42-82c5-98f005aab0f7
Córdova, Armando
d2a1239f-708d-4f9c-bf7c-c095e9a27cac
Ibrahem, Ismail
3cbac9c1-431b-4a1f-8c41-92aa617254b0
Zhao, Gui-Ling
106737c0-2aeb-4805-a8d7-496b1ce04322
Rios, Ramon
609bedf2-e886-4d62-a676-a32b6f8c1441
Vesely, Jan
1853ff19-a906-4321-bd69-f7e434176fc3
Sundén, Henrik
fe114b08-1de1-4e88-9778-a9cddf3aa76d
Dziedzic, Pawel
f1a3d742-6349-4e42-82c5-98f005aab0f7
Córdova, Armando
d2a1239f-708d-4f9c-bf7c-c095e9a27cac

Ibrahem, Ismail, Zhao, Gui-Ling, Rios, Ramon, Vesely, Jan, Sundén, Henrik, Dziedzic, Pawel and Córdova, Armando (2008) One-pot organocatalytic domino Michael/alpha-alkylation reactions: direct catalytic enantioselective cyclopropanation and cyclopentanation reactions. Chemistry - A European Journal, 14 (26), 7867-7879. (doi:10.1002/chem.200800442). (PMID:18618876)

Record type: Article

Abstract

The development of one-pot organocatalytic domino Michael/alpha-alkylation reactions between bromomalonates or bromoacetoacetate esters and alpha,beta-unsaturated aldehydes is presented. The chiral-amine-catalyzed reactions with bromomalonates as substrates give access to the corresponding 2-formylcyclopropane derivatives in high yields with excellent diastereoselectivity and up to 99 % ee. The catalytic domino Michael/alpha-alkylation reactions between 4-bromo-acetoacetate and enals provide a route for the synthesis of functionalized cyclopentanones in good to high yields with 93-99 % ee. The products from the organocatalytic reactions were also reduced with high diastereoselectivity to the corresponding cyclopropanols and cyclopentanols, respectively. Moreover, one-pot combinations of amine and heterocyclic carbene catalysis (AHCC) enabled the highly enantioselective synthesis of beta-malonate esters (91-97 % ee) from the reaction between bromomalonates and enals. The tandem catalysis included the catalytic domino reaction followed by catalytic in situ chemoselective ring-opening of the 2-formylcyclopropane intermediates.

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More information

e-pub ahead of print date: 11 July 2008
Published date: 8 September 2008
Keywords: unsaturated aldehydes, asymmetric catalysis, cyclopentanes, cyclopropanes, domino reactions, organocatalysis
Organisations: Chemistry

Identifiers

Local EPrints ID: 347773
URI: http://eprints.soton.ac.uk/id/eprint/347773
ISSN: 0947-6539
PURE UUID: bb15bd48-a8fb-4396-b5db-431e97f66235
ORCID for Ramon Rios: ORCID iD orcid.org/0000-0002-3843-8521

Catalogue record

Date deposited: 30 Jan 2013 09:47
Last modified: 17 Dec 2019 01:38

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Contributors

Author: Ismail Ibrahem
Author: Gui-Ling Zhao
Author: Ramon Rios ORCID iD
Author: Jan Vesely
Author: Henrik Sundén
Author: Pawel Dziedzic
Author: Armando Córdova

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