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Stereoselective inter- and intramolecular Pauson–Khand reactions of N-(2-alkynoyl) derivatives of chiral oxazolidin-2-ones

Stereoselective inter- and intramolecular Pauson–Khand reactions of N-(2-alkynoyl) derivatives of chiral oxazolidin-2-ones
Stereoselective inter- and intramolecular Pauson–Khand reactions of N-(2-alkynoyl) derivatives of chiral oxazolidin-2-ones
complete account of the intermolecular and intramolecular Pauson–Khand reactions of N-(2-alkynoyl) derivatives of chiral 2-oxazolidinones is presented. The intermolecular Pauson–Khand reactions with norbornene or norbornadiene take place under mild conditions and in high yields. Phenyl- or trimethylsilylpropiolate derivatives lead to the exclusive formation of 1,4-dicarbonyl regioisomers, while mixtures of 1,3- and 1,4-regioisomers are obtained with tetrolate derivatives. The diastereoselectivity of the reaction, determined by the substitution pattern of the oxazolidinone moieties, can be very high (up to 17.5:1 dr) for the formation of 1,4-dicarbonyl regioisomers, and the diastereomeric products can often be separated by column chromatography. Under the appropriate conditions, the intramolecular Pauson–Khand reactions of oxazolidinone-derived enynes can also take place with very good yields, but with low diastereoselectivities. The absolute configurations of several adducts have been determined, and the stereochemical outcome of the reaction has been rationalized.
alkyne complexes, asymmetric synthesis, chiral auxiliaries, cyclopentenones, pauson–khand reaction
1434-193X
3459-3478
Fonquerna, Sílvia
cd982dde-82df-487c-a8f0-38a4e8e9eae3
Rios, Ramon
609bedf2-e886-4d62-a676-a32b6f8c1441
Moyano, Albert
07f92405-40f4-4fc4-97b3-9bd5c9c14baa
Pericàs, Miquel A.
ab4d878b-95c0-4b5a-85ca-a59aa20eb420
Riera, Antoni
437f9024-e6c7-4ecd-ab9f-b6c2af66066a
Fonquerna, Sílvia
cd982dde-82df-487c-a8f0-38a4e8e9eae3
Rios, Ramon
609bedf2-e886-4d62-a676-a32b6f8c1441
Moyano, Albert
07f92405-40f4-4fc4-97b3-9bd5c9c14baa
Pericàs, Miquel A.
ab4d878b-95c0-4b5a-85ca-a59aa20eb420
Riera, Antoni
437f9024-e6c7-4ecd-ab9f-b6c2af66066a

Fonquerna, Sílvia, Rios, Ramon, Moyano, Albert, Pericàs, Miquel A. and Riera, Antoni (1999) Stereoselective inter- and intramolecular Pauson–Khand reactions of N-(2-alkynoyl) derivatives of chiral oxazolidin-2-ones. European Journal of Organic Chemistry, 1999 (12), 3459-3478. (doi:10.1002/(SICI)1099-0690(199912)1999:12<3459::AID-EJOC3459>3.0.CO;2-L).

Record type: Article

Abstract

complete account of the intermolecular and intramolecular Pauson–Khand reactions of N-(2-alkynoyl) derivatives of chiral 2-oxazolidinones is presented. The intermolecular Pauson–Khand reactions with norbornene or norbornadiene take place under mild conditions and in high yields. Phenyl- or trimethylsilylpropiolate derivatives lead to the exclusive formation of 1,4-dicarbonyl regioisomers, while mixtures of 1,3- and 1,4-regioisomers are obtained with tetrolate derivatives. The diastereoselectivity of the reaction, determined by the substitution pattern of the oxazolidinone moieties, can be very high (up to 17.5:1 dr) for the formation of 1,4-dicarbonyl regioisomers, and the diastereomeric products can often be separated by column chromatography. Under the appropriate conditions, the intramolecular Pauson–Khand reactions of oxazolidinone-derived enynes can also take place with very good yields, but with low diastereoselectivities. The absolute configurations of several adducts have been determined, and the stereochemical outcome of the reaction has been rationalized.

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More information

Published date: December 1999
Keywords: alkyne complexes, asymmetric synthesis, chiral auxiliaries, cyclopentenones, pauson–khand reaction
Organisations: Chemistry

Identifiers

Local EPrints ID: 348006
URI: http://eprints.soton.ac.uk/id/eprint/348006
ISSN: 1434-193X
PURE UUID: e4bdda45-2c7b-46e1-92fb-9c99289da09e
ORCID for Ramon Rios: ORCID iD orcid.org/0000-0002-3843-8521

Catalogue record

Date deposited: 05 Feb 2013 11:42
Last modified: 05 Nov 2019 01:39

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