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Title: Carbene-catalysed reductive coupling of nitrobenzyl bromides and activated ketones or imines via single-electron-transfer process
Authors: Li, Bao-Sheng
Wang, Yuhuang
Proctor, Rupert S. J.
Zhang, Yuexia
Webster, Richard D.
Yang, Song
Song, Baoan
Chi, Yonggui Robin
Keywords: Synthetic Chemistry Methodology
Issue Date: 2016
Source: Li, B.-S., Wang, Y., Proctor, R. S. J., Zhang, Y., Webster, R. D., Yang, S., et al. (2016). Carbene-catalysed reductive coupling of nitrobenzyl bromides and activated ketones or imines via single-electron-transfer process. Nature Communications, 7, 12933-.
Series/Report no.: Nature Communications
Abstract: Benzyl bromides and related molecules are among the most common substrates in organic synthesis. They are typically used as electrophiles in nucleophilic substitution reactions. These molecules can also be activated via single-electron-transfer (SET) process for radical reactions. Representative recent progress includes α-carbon benzylation of ketones and aldehydes via photoredox catalysis. Here we disclose the generation of (nitro)benzyl radicals via N-heterocyclic carbene (NHC) catalysis under reductive conditions. The radical intermediates generated via NHC catalysis undergo formal 1,2-addition with ketones to eventually afford tertiary alcohol products. The overall process constitutes a formal polarity-inversion of benzyl bromide, allowing a direct coupling of two initially electrophilic carbons. Our study provides a new carbene-catalysed reaction mode that should enable unconventional transformation of (nitro)benzyl bromides under mild organocatalytic conditions.
ISSN: 2041-1723
DOI: 10.1038/ncomms12933
Rights: © 2016 The Author(s). This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit
Fulltext Permission: open
Fulltext Availability: With Fulltext
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