Bromine-lithium exchange on gem-dibromoalkenes Part 1: batch vs microflow conditions
Bromine-lithium exchange on gem-dibromoalkenes Part 1: batch vs microflow conditions
The generation and reactivity of two model vinyl carbenoids from gem-dibromoalkenes 1 were studied in microflow systems. From substrate 1a (R = Ph, CF3), the lithium-bromine exchange could be simply performed within 30 ms at 20 °C with very good E-selectivity whereas the reaction was unselective under batch conditions, even at −78 °C. Moreover, the unstable carbenoid generated from 1b (R = Ph, H) could be trapped as the major product while only the Fritsch-Buttemberg-Wiechell rearrangement product was obtained in a flask under cryogenic conditions.
Fritsch-Buttemberg-Wiechell rearrangement, carbenoid, microfluidics, organolithium compounds, selectivity
139-143
Picard, Baptiste
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Perez, Katia
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Lebleu, Thomas
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Vuluga, Daniela
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Burel, Fabrice
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Harrowven, David C.
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Chataigner, Isabelle
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Maddaluno, Jacques
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Legros, Julien
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1 March 2020
Picard, Baptiste
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Perez, Katia
342362db-c394-4c54-aedd-df5f342bf1b8
Lebleu, Thomas
78571c1c-a9ea-4a45-b47e-cc76e2d0279d
Vuluga, Daniela
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Burel, Fabrice
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Harrowven, David C.
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Chataigner, Isabelle
13a550db-1647-4178-8200-f2547b148729
Maddaluno, Jacques
37e0bd01-a822-42e2-832d-69dc876fcefa
Legros, Julien
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Picard, Baptiste, Perez, Katia, Lebleu, Thomas, Vuluga, Daniela, Burel, Fabrice, Harrowven, David C., Chataigner, Isabelle, Maddaluno, Jacques and Legros, Julien
(2020)
Bromine-lithium exchange on gem-dibromoalkenes Part 1: batch vs microflow conditions.
Journal of Flow Chemistry, 10 (1), .
(doi:10.1007/s41981-019-00057-6).
Abstract
The generation and reactivity of two model vinyl carbenoids from gem-dibromoalkenes 1 were studied in microflow systems. From substrate 1a (R = Ph, CF3), the lithium-bromine exchange could be simply performed within 30 ms at 20 °C with very good E-selectivity whereas the reaction was unselective under batch conditions, even at −78 °C. Moreover, the unstable carbenoid generated from 1b (R = Ph, H) could be trapped as the major product while only the Fritsch-Buttemberg-Wiechell rearrangement product was obtained in a flask under cryogenic conditions.
Text
Dibromo-Part1-MS-Rev
- Accepted Manuscript
More information
Accepted/In Press date: 11 November 2019
e-pub ahead of print date: 14 February 2020
Published date: 1 March 2020
Additional Information:
Funding Information:
The authors gratefully acknowledge the European France-(Manche)-England cross-border cooperation program INTERREG IV A “AI-CHEM CHANNEL” and INTERREG V A “LABFACT”, co-financed by ERDF, for financial support. The authors from Normandie Université also thank the Tremplin Carnot I2C, the Labex SYNORG (ANR-11-LABX-0029) and the Région Normandie. K.P. is grateful to Ministerio de Educación Superior, Ciencia y Tecnología of the Dominican Republic for fellowship (CALIOPE programme). J.L. is grateful to Dr. M. De Paolis and Prof. H. Oulyadi for fruitful discussion and assistance.
Publisher Copyright:
© 2020, Akadémiai Kiadó.
Keywords:
Fritsch-Buttemberg-Wiechell rearrangement, carbenoid, microfluidics, organolithium compounds, selectivity
Identifiers
Local EPrints ID: 435913
URI: http://eprints.soton.ac.uk/id/eprint/435913
ISSN: 2062-249X
PURE UUID: 947cb347-5b49-45e3-bddd-fb47b431874e
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Date deposited: 22 Nov 2019 17:30
Last modified: 17 Mar 2024 05:03
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Contributors
Author:
Baptiste Picard
Author:
Katia Perez
Author:
Thomas Lebleu
Author:
Daniela Vuluga
Author:
Fabrice Burel
Author:
Isabelle Chataigner
Author:
Jacques Maddaluno
Author:
Julien Legros
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