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Bromine-lithium exchange on gem-dibromoalkenes part 1: batch vs microflow conditions

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.

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Scheme 1
Scheme 2

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Acknowledgements

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.

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Correspondence to Julien Legros.

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This article is dedicated to the memory of Prof. Jun-ichi Yoshida

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Picard, B., Pérez, K., Lebleu, T. et al. Bromine-lithium exchange on gem-dibromoalkenes part 1: batch vs microflow conditions. J Flow Chem 10, 139–143 (2020). https://doi.org/10.1007/s41981-019-00057-6

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Keywords

  • Fritsch-Buttemberg-Wiechell rearrangement
  • Carbenoid
  • Organolithium compounds
  • Selectivity
  • Microfluidics