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. 2019 Jul 5;21(13):5331-5334.
doi: 10.1021/acs.orglett.9b01957. Epub 2019 Jun 24.

Semiheterogeneous Dual Nickel/Photocatalytic (Thio)etherification Using Carbon Nitrides

Cristian Cavedon  1   2 , Amiera Madani  1   2 , Peter H Seeberger  1   2 , Bartholomäus Pieber  1
Affiliations

Semiheterogeneous Dual Nickel/Photocatalytic (Thio)etherification Using Carbon Nitrides

Cristian Cavedon et al. Org Lett. .

Abstract

A carbon nitride material can be combined with homogeneous nickel catalysts for light-mediated cross-couplings of aryl bromides with alcohols under mild conditions. The metal-free heterogeneous semiconductor is fully recyclable and couples a broad range of electron-poor aryl bromides with primary and secondary alcohols as well as water. The application for intramolecular reactions and the synthesis of active pharmaceutical ingredients was demonstrated. The catalytic protocol is applicable for the coupling of aryl iodides with thiols as well.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Examples of APIs containing the alkyl aryl ether motif.
Scheme 1
Scheme 1. Scope and Limitations of the Semiheterogeneous Etherification
Reaction conditions: aryl bromide (1.2 mmol), alcohol (2.4–4.8 mmol), CN-OA-m (20 mg), NiBr2·3H2O (120 μmol), dtbbpy (120 μmol), BIPA (6.0 mmol), MeCN (6.0 mL), white LEDs at 40 °C. Determined by 1H NMR using 1,3,5-trimethoxybenzene as internal standard. DMF was used as solvent.
Scheme 2
Scheme 2. Scope of Semiheterogeneous Thioetherification
Reaction conditions: methyl 4-iodobenzoate (1.2 mmol), thiol (2.4 mmol), CN-OA-m (20 mg), NiBr2·3H2O (120 μmol), dtbbpy (120 μmol), BIPA (6.0 mmol), MeCN (6.0 mL), white LEDs at 40 °C.
Figure 2
Figure 2
Recycling of CN-OA-m in the semiheterogeneous etherification.
See this image and copyright information in PMC

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