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Three- and four-membered rings from cycloadditions of 1,3-thiazolium-4-olates and aldehydes

Three- and four-membered rings from cycloadditions of 1,3-thiazolium-4-olates and aldehydes
Three- and four-membered rings from cycloadditions of 1,3-thiazolium-4-olates and aldehydes
2-Aminothioisomunchnones, a well-known family of masked dipoles, react with aromatic aldehydes in a domino cascade reaction that produces episulfides (thiiranes) or beta-lactams (2-azetidinones). This sequence is initiated by a [3+2] dipolar cycloaddition followed by ring opening of cycloadducts and intramolecular rearrangement to afford these unusual ring contractions. The nature of the reaction products depends on the structural characteristics of the starting dipole and the experimental conditions. Episulfides are obtained selectively as cis isomers with respect to both aryl groups, whereas beta-lactams are produced as cis/trans mixtures. These structural features were determined unequivocally by X-ray crystallographic analysis. The beta-lactams still possessed a flexible acyclic chain containing sulfur, a salient lead modification of the bioactive cyclic penems and cephems. The preferential production of exo transition structures was rationalized with the aid of computational calculations at the B3LYP/6-31G* level.
cycloaddition, domino reactions, episulfides, lactams, mesoionic, heterocyclescholesterol-absorption, diastereoselective synthesis, mesoioniccompounds, beta-lactams, inhibitors, thiiranes, 2-azetidinones, derivatives, chemistry, systems
0947-6539
3033-3042
Avalos, Martín
55d2a59e-8c35-4028-b6c5-bfdd7ecda5a4
Babiano, Reyes
b7ffd91c-bacd-4372-ab99-fc30ac2450ae
Cintas, Pedro
29979233-8382-47a8-bde7-1faf4869308c
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Jiménez, José L.
074cc8fd-9ea1-41fc-b8b6-551d26e5fcd3
Light, Mark E.
cf57314e-6856-491b-a8d2-2dffc452e161
López, Ignacio
215a6254-7805-40e9-a90d-878a966e6dbb
Palacios, Juan C.
2c06e379-89b3-46b1-95c8-7f5057732f9f
Silvero, Guadalupe
8e6975cc-88ec-4809-8040-bc84413d57d6
Avalos, Martín
55d2a59e-8c35-4028-b6c5-bfdd7ecda5a4
Babiano, Reyes
b7ffd91c-bacd-4372-ab99-fc30ac2450ae
Cintas, Pedro
29979233-8382-47a8-bde7-1faf4869308c
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Jiménez, José L.
074cc8fd-9ea1-41fc-b8b6-551d26e5fcd3
Light, Mark E.
cf57314e-6856-491b-a8d2-2dffc452e161
López, Ignacio
215a6254-7805-40e9-a90d-878a966e6dbb
Palacios, Juan C.
2c06e379-89b3-46b1-95c8-7f5057732f9f
Silvero, Guadalupe
8e6975cc-88ec-4809-8040-bc84413d57d6

Avalos, Martín, Babiano, Reyes, Cintas, Pedro, Hursthouse, Michael B., Jiménez, José L., Light, Mark E., López, Ignacio, Palacios, Juan C. and Silvero, Guadalupe (2001) Three- and four-membered rings from cycloadditions of 1,3-thiazolium-4-olates and aldehydes. Chemistry - A European Journal, 7 (14), 3033-3042. (doi:10.1002/1521-3765(20010716)7:14<3033::AID-CHEM3033>3.0.CO;2-F).

Record type: Article

Abstract

2-Aminothioisomunchnones, a well-known family of masked dipoles, react with aromatic aldehydes in a domino cascade reaction that produces episulfides (thiiranes) or beta-lactams (2-azetidinones). This sequence is initiated by a [3+2] dipolar cycloaddition followed by ring opening of cycloadducts and intramolecular rearrangement to afford these unusual ring contractions. The nature of the reaction products depends on the structural characteristics of the starting dipole and the experimental conditions. Episulfides are obtained selectively as cis isomers with respect to both aryl groups, whereas beta-lactams are produced as cis/trans mixtures. These structural features were determined unequivocally by X-ray crystallographic analysis. The beta-lactams still possessed a flexible acyclic chain containing sulfur, a salient lead modification of the bioactive cyclic penems and cephems. The preferential production of exo transition structures was rationalized with the aid of computational calculations at the B3LYP/6-31G* level.

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More information

Published date: 2001
Keywords: cycloaddition, domino reactions, episulfides, lactams, mesoionic, heterocyclescholesterol-absorption, diastereoselective synthesis, mesoioniccompounds, beta-lactams, inhibitors, thiiranes, 2-azetidinones, derivatives, chemistry, systems

Identifiers

Local EPrints ID: 19386
URI: https://eprints.soton.ac.uk/id/eprint/19386
ISSN: 0947-6539
PURE UUID: 1be32e80-04bd-4eb5-a794-c51ba93d11f3
ORCID for Mark E. Light: ORCID iD orcid.org/0000-0002-0585-0843

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Date deposited: 13 Feb 2006
Last modified: 20 Jul 2019 01:10

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Contributors

Author: Martín Avalos
Author: Reyes Babiano
Author: Pedro Cintas
Author: José L. Jiménez
Author: Mark E. Light ORCID iD
Author: Ignacio López
Author: Juan C. Palacios
Author: Guadalupe Silvero

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