Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2018 Oct 30:14:2730-2736.
doi: 10.3762/bjoc.14.251. eCollection 2018.

Photocatalyic Appel reaction enabled by copper-based complexes in continuous flow

Clémentine Minozzi  1 , Jean-Christophe Grenier-Petel  1 , Shawn Parisien-Collette  1 , Shawn K Collins  1
Affiliations

Photocatalyic Appel reaction enabled by copper-based complexes in continuous flow

Clémentine Minozzi et al. Beilstein J Org Chem. .

Abstract

A copper-based photocatalyst, Cu(tmp)(BINAP)BF4, was found to be active in a photoredox Appel-type conversion of alcohols to bromides. The catalyst was identified from a screening of 50 complexes and promoted the transformation of primary and secondary alcohols to their corresponding bromides and carboxylic acids to their anhydrides. The protocol was also amendable and optimized under continuous flow conditions.

Keywords: Appel; continuous flow; copper; halides; photocatalysis.

PubMed Disclaimer

Figures

Figure 1
Figure 1
Alcohol→bromide functional group transformations.
Figure 2
Figure 2
Ligands used in the library generation of heteroleptic copper(I)-based complexes for photocatalysis.
Figure 3
Figure 3
Evaluation of the library of copper-based complexes in photocatalytic alcohol→bromide conversion. Reactions irradiated with 394 nm light (pink) or 450 nm (blue). Front entries without an indicated phosphine ligand pertain to homoleptic Cu(diamine)2BF4 complexes and are colored in lighter blue. Entries without a color indicate reactions which could not be performed due to solubility or overoxidation of the complex.
Figure 4
Figure 4
Experimental set-up for the photocatalytic conversion of alcohols to bromides. PFA tubing is wrapped around purple LEDs (394 nm) and fans are placed underneath reactors to maintain cooling.
Scheme 1
Scheme 1
Copper-based photocatalysis for photocatalytic synthesis of an anhydride.
See this image and copyright information in PMC

References

    1. Stephenson C R J, Yoon T P, MacMillan D W C, editors. Visible Light Photocatalysis in Organic Chemistry. Hoboken, New Jersey: Wiley-VCH; 2018.
    1. Albini A, Fagnoni M, editors. Handbook of Synthetic Photochemistry. Germany: Wiley-VCH; 2010.
    1. Rackl D, Kreitmeier P, Reiser O. Green Chem. 2016;18:214–219. doi: 10.1039/C5GC01792K. - DOI
    1. Lima C G S, de M. Lima T, Duarte M, Jurberg I D, Paixão M W. ACS Catal. 2016;6:1389–1407. doi: 10.1021/acscatal.5b02386. - DOI
    1. Appel R. Angew Chem, Int Ed Engl. 1975;14:801–811. doi: 10.1002/anie.197508011. - DOI

LinkOut - more resources