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. 2022 Sep 9;61(44):e202210508.
doi: 10.1002/anie.202210508. Online ahead of print.

Temperature-Controlled Mechanochemistry for the Nickel-Catalyzed Suzuki-Miyaura-Type Coupling of Aryl Sulfamates via Ball Milling and Twin-Screw Extrusion

Robert R A Bolt  1 , Sarah E Raby-Buck  1 , Katharine Ingram  2 , Jamie A Leitch  1 , Duncan L Browne  1
Affiliations

Temperature-Controlled Mechanochemistry for the Nickel-Catalyzed Suzuki-Miyaura-Type Coupling of Aryl Sulfamates via Ball Milling and Twin-Screw Extrusion

Robert R A Bolt et al. Angew Chem Int Ed Engl. .

Abstract
in English, German

The nickel catalyzed Suzuki-Miyaura-type coupling of aryl sulfamates and boronic acid derivatives enabled by temperature-controlled mechanochemistry via the development of a programmable PID-controlled jar heater is reported. This base-metal-catalyzed, solvent-free, all-under-air protocol was also scaled 200-fold using twin-screw extrusion technology affording decagram quantities of material.

The use of temperature-controlled mechanochemistry to enable the mechanochemical nickel-catalyzed Suzuki-Miyaura coupling is herein described. Transitioning from a capricious room-temperature protocol, through to a heated, PID-controlled programmable jar heater manifold was required to deliver an efficient method for the coupling of aryl sulfamates (derived from ubiquitous phenols) and aryl boronic acid species. Furthermore, this process is conducted using a base-metal nickel catalyst, in the absence of bulk solvent, and in the absence of air/moisture sensitive reaction set-ups. This methodology is showcased through translation to large-scale twin-screw extrusion methodology enabling 200-fold scale increase, producing decagram quantities of C−C coupled material.

Keywords: Cross-Coupling; Mechanochemistry; Nickel Catalysis; Twin-Screw Extrusion.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Suzuki–Miyaura‐type cross coupling in mechanochemistry. A) Room temperature coupling using palladium catalysis. B) High‐temperature Suzuki–Miyaura coupling. C) This work on temperature‐controlled nickel catalysis with phenol derivatives.
Scheme 2
Scheme 2
Initial studies into the nickel‐catalyzed Suzuki‐type coupling of activated phenols. A) Exploration of different activating groups for phenols. B) Preliminary scope on small selection of sulfamates and aryl boronic acids. C) Investigations into the profound difference in efficiency of different jar sizes.
Scheme 3
Scheme 3
Temperature‐controlled Suzuki–Miyaura coupling. A) Evolution of heating devices in temperature‐controlled mechanochemistry from heat gun to PID‐controlled jar heater. B) Schematic and pictorial overview of the prototyped jar heater. C) Results from different heating protocols on subset of compounds. D) Fine‐tuning of heating profile for the Suzuki–Miyaura cross‐coupling. a Jar temperature produced by latent heat of milling after 30 minutes reaction time. b Conditions as per top left of scheme – numbers given are calculated via 1H NMR analysis of the crude reaction mixture against mesitylene as an internal standard.
Scheme 4
Scheme 4
Scope of the temperature‐controlled mechanochemical nickel‐catalyzed Suzuki–Miyaura‐type coupling. A) Boronic acid scope. B) Sulfamate scope. C) Revisiting activated phenol scope. a 1H NMR yield calculated vs. mesitylene as an internal standard.
Scheme 5
Scheme 5
Upscaling the mechanochemical nickel‐catalyzed Suzuki–Miyaura coupling via twin‐screw extrusion. A) In depth protocol design. B) Pictorial representation of extrusion run. C) Results from the 100 mmol‐scale extrusion process including data on throughput rate and space time yield (STY).
See this image and copyright information in PMC

References

    1. None
    1. Suzuki A., Angew. Chem. Int. Ed. 2011, 50, 6722–6737; - PubMed
    2. Angew. Chem. 2011, 123, 6854–6869;
    1. Miyaura N., Suzuki A., Chem. Rev. 1995, 95, 2457–2483.
    1. None
    1. “Suzuki–Miyaura Coupling”: Blakemore D. C. in Synthetic Methods in Drug Discovery, Vol. 1 (Eds.: Blakemore D. C., Doyle P., Fobian Y. M.), Royal Society of Chemistry, London, 2016, chap. 1, pp. 1–69;

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