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Mechanism and origins of stereoselectivity of the aldol-tishchenko reaction of sulfinimines

Mechanism and origins of stereoselectivity of the aldol-tishchenko reaction of sulfinimines
Mechanism and origins of stereoselectivity of the aldol-tishchenko reaction of sulfinimines

Density functional theory computations have elucidated the mechanism and origins of stereoselectivity in McGlacken's aldol-Tishchenko reaction for the diastereoselective synthesis of 1,3-amino alcohols using Ellman's t-butylsulfinimines as chiral auxiliaries. Variations of stereochemical outcome are dependent on the nature of the ketone starting materials used, and the aspects leading to these differences have been rationalized. The intramolecular hydride transfer step is the rate- and stereochemistry-determining step, and all prior steps are reversible.

Aldehydes, Imines, Ketones, Stereoisomerism, Sulfonium Compounds
0022-3263
4296-4303
Turlik, Aneta
cb9c3da1-2729-47ce-9c13-883d033843c5
Ando, Kaori
91358af5-39e6-4045-bc9d-32741a444574
Mackey, Pamela
8817de93-dc6b-4d93-bfa5-8409929bf955
Alcock, Emma
b60352b8-fda7-4bd5-89a2-ca407d176b9e
Light, Mark
cf57314e-6856-491b-a8d2-2dffc452e161
McGlacken, Gerard P.
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Houk, K. N.
038f0df8-ab7f-4bcc-87ce-53342be57e23
Turlik, Aneta
cb9c3da1-2729-47ce-9c13-883d033843c5
Ando, Kaori
91358af5-39e6-4045-bc9d-32741a444574
Mackey, Pamela
8817de93-dc6b-4d93-bfa5-8409929bf955
Alcock, Emma
b60352b8-fda7-4bd5-89a2-ca407d176b9e
Light, Mark
cf57314e-6856-491b-a8d2-2dffc452e161
McGlacken, Gerard P.
7232768a-94ff-4794-81b3-1467726505e0
Houk, K. N.
038f0df8-ab7f-4bcc-87ce-53342be57e23

Turlik, Aneta, Ando, Kaori, Mackey, Pamela, Alcock, Emma, Light, Mark, McGlacken, Gerard P. and Houk, K. N. (2021) Mechanism and origins of stereoselectivity of the aldol-tishchenko reaction of sulfinimines. Journal of Organic Chemistry, 86 (5), 4296-4303. (doi:10.1021/acs.joc.0c02862).

Record type: Article

Abstract

Density functional theory computations have elucidated the mechanism and origins of stereoselectivity in McGlacken's aldol-Tishchenko reaction for the diastereoselective synthesis of 1,3-amino alcohols using Ellman's t-butylsulfinimines as chiral auxiliaries. Variations of stereochemical outcome are dependent on the nature of the ketone starting materials used, and the aspects leading to these differences have been rationalized. The intramolecular hydride transfer step is the rate- and stereochemistry-determining step, and all prior steps are reversible.

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More information

e-pub ahead of print date: 15 February 2021
Published date: 5 March 2021
Additional Information: Funding Information: The authors are grateful to the National Science Foundation (grant CHE-1764328), the Irish Research Council (IRC GOIPG/2014/343 and GOIPG/2017/7), and the Science Foundation Ireland (09/RFP/CHS2353, SFI/12/IP/1315 and SFI/12/RC/2275). Calculations were performed on the Hoffman2 cluster at the University of California, Los Angeles, and the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by the National Science Foundation (grant OCI-1053575). Publisher Copyright: © Copyright: Copyright 2021 Elsevier B.V., All rights reserved.
Keywords: Aldehydes, Imines, Ketones, Stereoisomerism, Sulfonium Compounds

Identifiers

Local EPrints ID: 451051
URI: http://eprints.soton.ac.uk/id/eprint/451051
ISSN: 0022-3263
PURE UUID: a6bc12d8-a52f-47ec-b099-ea22837ceb25
ORCID for Mark Light: ORCID iD orcid.org/0000-0002-0585-0843

Catalogue record

Date deposited: 03 Sep 2021 16:44
Last modified: 26 Nov 2021 02:42

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Contributors

Author: Aneta Turlik
Author: Kaori Ando
Author: Pamela Mackey
Author: Emma Alcock
Author: Mark Light ORCID iD
Author: Gerard P. McGlacken
Author: K. N. Houk

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