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Chiral N-acyloxazolidines: synthesis, structure, and mechanistic insights

Chiral N-acyloxazolidines: synthesis, structure, and mechanistic insights
Chiral N-acyloxazolidines: synthesis, structure, and mechanistic insights
A series of chiral imines derived from 1-amino-1-deoxyalditols such as D-glucamine, a rather unexplored raw material from the chiral pool, have been serendipitiously transformed into a novel family of N-acetyl-1,3-oxazolidines by means of an unexpected acetylation. The structure of these substances is supported by spectroscopic and crystallographic data. The acetylates also trigger a complex dynamic transformation, in which an initially configured trans oxazolidine converts into a more stable cis-configured derivative. Both isomers can also exist as rotational conformers (E,Z) as a consequence of the restricted rotation around the N-acetyl bond. The barriers to rotation have been determined by variable-temperature experiments. Overall, this transformation most likely involves the intermediacy of a chiral iminium ion, which has been documented in the synthesis of nitrogen heterocycles, thus explaining the experimental facts.
ugi-synthesis, atom, stereoselective synthesis, carbohydrate, templates, diastereoselective synthesis, staudinger reaction, ring-chain tautomerism, asymmetric-synthesis, economy, alpha-amino-acids, d-glucosamine
0022-3263
661-672
Avalos, M.
d6c0ff76-2d77-4fe6-89b5-463404a42de0
Babiano, R.
d79f2a4d-a2e3-4f73-8e58-65eee2a9f88a
Cintas, P.
d4420202-106c-4e8a-b903-5deef99e6a39
Jimenez, J.L.
b07affd8-4345-44a9-b7b0-582c0d76bcf7
Light, M.E.
cf57314e-6856-491b-a8d2-2dffc452e161
Palacios, J.C.
db0e8c94-0385-4349-91a1-b0b2e03f4aab
Perez, E.M.S.
f5112b4f-6597-408a-b0ab-b20ec58cdea7
Avalos, M.
d6c0ff76-2d77-4fe6-89b5-463404a42de0
Babiano, R.
d79f2a4d-a2e3-4f73-8e58-65eee2a9f88a
Cintas, P.
d4420202-106c-4e8a-b903-5deef99e6a39
Jimenez, J.L.
b07affd8-4345-44a9-b7b0-582c0d76bcf7
Light, M.E.
cf57314e-6856-491b-a8d2-2dffc452e161
Palacios, J.C.
db0e8c94-0385-4349-91a1-b0b2e03f4aab
Perez, E.M.S.
f5112b4f-6597-408a-b0ab-b20ec58cdea7

Avalos, M., Babiano, R., Cintas, P., Jimenez, J.L., Light, M.E., Palacios, J.C. and Perez, E.M.S. (2007) Chiral N-acyloxazolidines: synthesis, structure, and mechanistic insights. Journal of Organic Chemistry, 73 (2), 661-672. (doi:10.1021/jo702149m).

Record type: Article

Abstract

A series of chiral imines derived from 1-amino-1-deoxyalditols such as D-glucamine, a rather unexplored raw material from the chiral pool, have been serendipitiously transformed into a novel family of N-acetyl-1,3-oxazolidines by means of an unexpected acetylation. The structure of these substances is supported by spectroscopic and crystallographic data. The acetylates also trigger a complex dynamic transformation, in which an initially configured trans oxazolidine converts into a more stable cis-configured derivative. Both isomers can also exist as rotational conformers (E,Z) as a consequence of the restricted rotation around the N-acetyl bond. The barriers to rotation have been determined by variable-temperature experiments. Overall, this transformation most likely involves the intermediacy of a chiral iminium ion, which has been documented in the synthesis of nitrogen heterocycles, thus explaining the experimental facts.

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More information

Published date: 2007
Keywords: ugi-synthesis, atom, stereoselective synthesis, carbohydrate, templates, diastereoselective synthesis, staudinger reaction, ring-chain tautomerism, asymmetric-synthesis, economy, alpha-amino-acids, d-glucosamine

Identifiers

Local EPrints ID: 54417
URI: http://eprints.soton.ac.uk/id/eprint/54417
ISSN: 0022-3263
PURE UUID: f3f21b79-72d0-4208-9d15-b8838ca513b4
ORCID for M.E. Light: ORCID iD orcid.org/0000-0002-0585-0843

Catalogue record

Date deposited: 31 Jul 2008
Last modified: 16 Mar 2024 03:04

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Contributors

Author: M. Avalos
Author: R. Babiano
Author: P. Cintas
Author: J.L. Jimenez
Author: M.E. Light ORCID iD
Author: J.C. Palacios
Author: E.M.S. Perez

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