Scale-Up of Continuous Metallaphotoredox Catalyzed C–O Coupling to a 10 kg-Scale Using Small Footprint Photochemical Taylor Vortex Flow Reactors DOI

Rodolfo I. Teixeira,

Toby H. Waldron Clarke,

Ashley Love

и другие.

Organic Process Research & Development, Год журнала: 2024, Номер 29(1), С. 34 - 47

Опубликована: Дек. 4, 2024

We report the development and optimization of a scalable flow process for metallaphotoredox (Ir/Ni) C-O coupling, mild efficient approach forming alkyl-aryl ethers, common motif in medicinal chemistry settings. Time-resolved infrared spectroscopy (TRIR) highlighted amine as major quencher photocatalyst triplet excited state, along with formation an Ir(II) species that, presence Ni cocatalyst, has its lifetime shortened, suggesting reductive quenching Ir(III)*, followed by reoxidation facilitated cocatalyst. TRIR batch reaction screening was used to develop conditions transferrable flow, many processing benefits performing were then demonstrated using simple construct/operate, small-footprint FEP coil reactor, including short (<10 min) space times reduced catalyst loadings (down 0.1 mol % Ir, 1 Ni) while retaining good yield/conversion. Scalability increasing length or diameter reactor tubing, however, due suspected mass transfer/mixing limitations, yield decreased upon scale-up some cases. Therefore, we applied modified version our previously reported photochemical Taylor Vortex Flow Reactor (PhotoVortex), where vortices short-irradiated path allow reactions be performed efficiently via excellent mixing. In small PhotoVortex (8 mL irradiated volume), have projected productivities around kg day-1 >10 large (185 volume) product yields (>90%) low (0.1 0.5 [Ir{dF(CF3)ppy}2dtbbpy]PF6), enabled mixing ensuring sufficient transfer between short-lived photoexcited other transient species.

Язык: Английский

Process Intensification of the Continuous Synthesis of Bio-Derived Monomers for Sustainable Coatings Using a Taylor Vortex Flow Reactor DOI Creative Commons

Matthew D. Edwards,

Matthew T. Pratley, Charles M. Gordon

и другие.

Organic Process Research & Development, Год журнала: 2024, Номер 28(5), С. 1917 - 1928

Опубликована: Май 9, 2024

We describe the optimization and scale-up of two consecutive reaction steps in synthesis bio-derived alkoxybutenolide monomers that have been reported as potential replacements for acrylate-based coatings ( Sci. Adv. 2020, 6, eabe0026). These are synthesized by (i) oxidation furfural with photogenerated singlet oxygen followed (ii) thermal condensation desired 5-hydroxyfuranone intermediate product an alcohol, a step which until now has involved lengthy batch reaction. The successfully telescoped into single kilogram-scale process without any need to isolate between steps. Our development FTIR monitoring, data analysis via 2D visualization, different photoreactors: semicontinuous photoreactor based on modified rotary evaporator, where correlation spectroscopy (2D-COS) revealed loss methyl formate coproduct, our fully continuous Taylor Vortex photoreactor, enhanced mass transfer permitted use near-stoichiometric equivalents O2. in-line monitoring modeling greatly accelerated reactor. This led photo-oxidation 85% yield projected productivity 1.3 kg day–1 space-time 0.06 mol mL–1. Higher productivities could be achieved while sacrificing (e.g., 4 at 40% yield). superheated methanol 200 °C pressurized flow reactor second step, 5-hydroxyfuranone, from 20 h reflux (0.5 L, 85 g) space time <1 min only 3 mL volume operating >700 g day–1. Proof concept telescoping was established overall two-step 67%, producing 1.1 methoxybutenolide monomer purification intermediate.

Язык: Английский

Процитировано

10
Open-source 3D printed reactors for reproducible batch and continuous-flow photon-induced chemistry: design and characterization DOI Creative Commons
Tom M. Masson, Stefan D. A. Zondag, J. Schuurmans

и другие.

Reaction Chemistry & Engineering, Год журнала: 2024, Номер 9(8), С. 2218 - 2225

Опубликована: Янв. 1, 2024

From screening conditions in batch to scaling up continuous flow, we offer photochemical systems tailored your needs. Simply download the files and start printing!

Язык: Английский

Процитировано

4
Mechanometallaphotoredox Catalysis: Utilizing Increased Throughput Mechanochemistry to Develop Solvent-Minimized Aryl Amination and C(sp2)-C(sp3) Cross-Coupling Reactions with Increased Tolerance to Aerobic Conditions DOI Creative Commons
Francis Millward, Eli Zysman‐Colman

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Май 22, 2025

Photocatalysis as a tool used in organic synthesis has predominantly relied on the use of solvents, be it under homogeneous or heterogeneous conditions. In particular, metallaphotoredox catalysis reactions commonly toxic solvents such DMA and DMF. Herein, we demonstrate how mechanophotocatalysis, synergistic union mechanochemistry photocatalysis, is compatible with this class dual involving both photocatalyst nickel(II) cocatalysts. Using ball milling, these mechanistically complex can conducted absence bulk solvent air, affording high-yielding aryl aminations C(sp2)-C(sp3) cross-couplings alkyl carboxylic acids, trifluoroborate salts, bromides. These advances are facilitated by introduction novel reaction vessel design for conducting four mechanophotocatalysis simultaneously. This work highlights promise solvent-minimized photocatalysis reactions, demonstrating that examples redundant, thus significantly reducing waste stream. Through time-resolved photoluminescence studies, observed excited states five different photocatalysts were quenched oxygen more solution than solid state, providing evidence origin increased tolerance to aerobic conditions experience.

Язык: Английский

Процитировано

0
Scale-Up of Continuous Metallaphotoredox Catalyzed C–O Coupling to a 10 kg-Scale Using Small Footprint Photochemical Taylor Vortex Flow Reactors DOI

Rodolfo I. Teixeira,

Toby H. Waldron Clarke,

Ashley Love

и другие.

Organic Process Research & Development, Год журнала: 2024, Номер 29(1), С. 34 - 47

Опубликована: Дек. 4, 2024

We report the development and optimization of a scalable flow process for metallaphotoredox (Ir/Ni) C-O coupling, mild efficient approach forming alkyl-aryl ethers, common motif in medicinal chemistry settings. Time-resolved infrared spectroscopy (TRIR) highlighted amine as major quencher photocatalyst triplet excited state, along with formation an Ir(II) species that, presence Ni cocatalyst, has its lifetime shortened, suggesting reductive quenching Ir(III)*, followed by reoxidation facilitated cocatalyst. TRIR batch reaction screening was used to develop conditions transferrable flow, many processing benefits performing were then demonstrated using simple construct/operate, small-footprint FEP coil reactor, including short (<10 min) space times reduced catalyst loadings (down 0.1 mol % Ir, 1 Ni) while retaining good yield/conversion. Scalability increasing length or diameter reactor tubing, however, due suspected mass transfer/mixing limitations, yield decreased upon scale-up some cases. Therefore, we applied modified version our previously reported photochemical Taylor Vortex Flow Reactor (PhotoVortex), where vortices short-irradiated path allow reactions be performed efficiently via excellent mixing. In small PhotoVortex (8 mL irradiated volume), have projected productivities around kg day-1 >10 large (185 volume) product yields (>90%) low (0.1 0.5 [Ir{dF(CF3)ppy}2dtbbpy]PF6), enabled mixing ensuring sufficient transfer between short-lived photoexcited other transient species.

Язык: Английский

Процитировано

1