Multigram Copper-Catalyzed Azidodeboronation of Alkenyl Boronates
- 1Enamine Ltd., Winston Churchill Street 78, Kyїv, Ukraine, 02094
- 2Taras Shevchenko National University of Kyiv, Volodymyrska Street 60, Kyїv, Ukraine, 01601
- 3Enamine Scientific Research Institute, Winston Churchill Street 67, Kyїv, Ukraine
Abstract
A multigram synthetic approach to alkenyl azides based on copper-catalyzed azidodeboronation of alkenyl pinacol boronates was described. The optimized protocol relied on the use of Cu(OAc) 2 as the reaction promoter, which provided higher, reproducible yields and did not cause uncontrolled decomposition of the reaction mixture, unlike the CuSO 4 ·5H 2 O-based protocol reported previously. The method was applicable to β-, β,β-, and α,β-substituted substrates, including those bearing electron-withdrawing groups and saturated O -, N -, and S -heterocyclic motifs. Some alkenyl azides were prepared on up to 21 g scale, and their thermal behavior was evaluated by thermogravimetric analysis. The synthetic utility of the products was demonstrated through the preparation of a substituted pyrrole and 1-alkenyl-1,2,3-triazoles. Furthermore, a one-pot azidation – click reaction protocol enabled the direct conversion of alkenyl boronates into the corresponding triazoles without isolation of unstable or highly volatile alkenyl azide intermediates, thereby broadening the accessible substrate scope.
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BibTeX
@misc{kovalenko2026multigram,
title = {{Multigram Copper-Catalyzed Azidodeboronation of Alkenyl Boronates}},
author = {Maksym Kovalenko and Yevhen M. Ivon and Yaroslava Kovalchuk and Kristina Bakhmatska and Dmytrii Kryvenchuk and Yaroslav Yakivets and Daria S. Klymenko and Oleksandr S. Liashuk and Oleksandr O. Grygorenko},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15009735/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009735/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Multigram Copper-Catalyzed Azidodeboronation of Alkenyl Boronates
AU - Maksym Kovalenko
AU - Yevhen M. Ivon
AU - Yaroslava Kovalchuk
AU - Kristina Bakhmatska
AU - Dmytrii Kryvenchuk
AU - Yaroslav Yakivets
AU - Daria S. Klymenko
AU - Oleksandr S. Liashuk
AU - Oleksandr O. Grygorenko
PY - 2026
DA - 2026/10/01
PB - ChemRxiv
DO - 10.26434/chemrxiv.15009735/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009735/v1
AB - A multigram synthetic approach to alkenyl azides based on copper-catalyzed azidodeboronation of alkenyl pinacol boronates was described. The optimized protocol relied on the use of Cu(OAc) 2 as the reaction promoter, which provided higher, reproducible yields and did not cause uncontrolled decomposition of the reaction mixture, unlike the CuSO 4 ·5H 2 O-based protocol reported previously. The method was applicable to β-, β,β-, and α,β-substituted substrates, including those bearing electron-withdrawing groups and saturated O -, N -, and S -heterocyclic motifs. Some alkenyl azides were prepared on up to 21 g scale, and their thermal behavior was evaluated by thermogravimetric analysis. The synthetic utility of the products was demonstrated through the preparation of a substituted pyrrole and 1-alkenyl-1,2,3-triazoles. Furthermore, a one-pot azidation – click reaction protocol enabled the direct conversion of alkenyl boronates into the corresponding triazoles without isolation of unstable or highly volatile alkenyl azide intermediates, thereby broadening the accessible substrate scope.
ER -