Organocatalytic asymmetric electrochemical synthesis of epibromohydrins from allylic alcohols
- 1Jiangsu Key Laboratory of Advanced Catalytic Materials & Technology, School of Petrochemical Engineering, Changzhou University Changzhou 213164 China
- 2Department of Chemistry, The Hong Kong University of Science and Technology Clear Water Bay Kowloon Hong Kong SAR 999077 China
Abstract
Optically active epibromohydrins represent a structurally privileged family of chiral building blocks, yet their asymmetric synthesis remains hampered by a reliance on stoichiometric chemical oxidants and multi-step protocols. Herein, we report an organocatalytic asymmetric electrochemical bromoetherification of allylic tertiary alcohols that constructs these densely functionalized scaffolds in a single operational step. By merging interfacial electrosynthesis with a synergistic chiral phase-transfer catalyst (PTC) and chiral phosphoric acid (CPA) counter anion framework, the high reactivity of electrogenerated Br2 species is tightly regulated, successfully suppressing unselective, racemic background pathways. Utilizing inexpensive NaBr as the bromine source in a DCM/H2O biphasic system, a range of allylic tertiary alcohols were smoothly converted into the corresponding bromoepoxides in high yields and with high enantioselectivities. Control experiments and cyclic voltammetry studies suggested that stereocontrol is sensitive to the balance between anodic bromide generation and phase-transfer-mediated trapping. This strategy is complementary to the conventional synthesis of epibromohydrins by chemical oxidation.
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BibTeX
@article{han2026organocatalytic,
title = {{Organocatalytic asymmetric electrochemical synthesis of epibromohydrins from allylic alcohols}},
author = {Zhengyu Han and Ming Fang and Peinan Shang and Shuxuan Liu and Hai Huang and Jianwei Sun},
journal = {Chemical Science},
year = {2026},
month = aug,
doi = {10.1039/d6sc05589c},
url = {https://doi.org/10.1039/d6sc05589c},
note = {CC BY 3.0},
}
RIS
TY - JOUR
TI - Organocatalytic asymmetric electrochemical synthesis of epibromohydrins from allylic alcohols
AU - Zhengyu Han
AU - Ming Fang
AU - Peinan Shang
AU - Shuxuan Liu
AU - Hai Huang
AU - Jianwei Sun
PY - 2026
DA - 2026/08/31
JO - Chemical Science
DO - 10.1039/d6sc05589c
UR - https://doi.org/10.1039/d6sc05589c
AB - Optically active epibromohydrins represent a structurally privileged family of chiral building blocks, yet their asymmetric synthesis remains hampered by a reliance on stoichiometric chemical oxidants and multi-step protocols. Herein, we report an organocatalytic asymmetric electrochemical bromoetherification of allylic tertiary alcohols that constructs these densely functionalized scaffolds in a single operational step. By merging interfacial electrosynthesis with a synergistic chiral phase-transfer catalyst (PTC) and chiral phosphoric acid (CPA) counter anion framework, the high reactivity of electrogenerated Br2 species is tightly regulated, successfully suppressing unselective, racemic background pathways. Utilizing inexpensive NaBr as the bromine source in a DCM/H2O biphasic system, a range of allylic tertiary alcohols were smoothly converted into the corresponding bromoepoxides in high yields and with high enantioselectivities. Control experiments and cyclic voltammetry studies suggested that stereocontrol is sensitive to the balance between anodic bromide generation and phase-transfer-mediated trapping. This strategy is complementary to the conventional synthesis of epibromohydrins by chemical oxidation.
SN - 2041-6520
SN - 2041-6539
ER -