Optimization of a Decatungstate-Catalyzed C(sp3)–H Alkylation Using a Continuous Oscillatory Millistructured Photoreactor

Zhenghui Wen; A. Maheshwari; Carlo Sambiagio; Yuchao Deng; Gabriele Laudadio; Koen Van Aken; Yuhan Sun; H.P.L. Gemoets; Timothy Noël

doi:10.1021/acs.oprd.0c00235

Optimization of a Decatungstate-Catalyzed C(sp3)–H Alkylation Using a Continuous Oscillatory Millistructured Photoreactor

Zhenghui Wen, A. Maheshwari, Carlo Sambiagio, Yuchao Deng, Gabriele Laudadio, Koen Van Aken, Yuhan Sun, H.P.L. Gemoets, Timothy Noël (Corresponding author)

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Abstract

Tetrabutylammonium decatungstate (TBADT) has emerged as an efficient and versatile photocatalyst for hydrogen atom transfer (HAT) processes that enables the cleavage of both activated and unactivated aliphatic C–H bonds. Using a recently developed oscillatory millistructured continuous-flow photoreactor, investigations of a decatungstate-catalyzed C(sp3)–H alkylation protocol were carried out, and the results are presented here. The performance of the reactor was evaluated in correlation to several chemical and process parameters, including residence time, light intensity, catalyst loading, and substrate/reagent concentration. In comparison with previously reported batch and flow protocols, conditions were found that led to considerably higher productivity, achieving a throughput up to 36.7 mmol/h with a residence time of only 7.5 min.

Original language	English
Pages (from-to)	2356-2361
Number of pages	6
Journal	Organic Process Research & Development
Volume	24
Issue number	10
Early online date	2020
DOIs	https://doi.org/10.1021/acs.oprd.0c00235
Publication status	Published - 16 Oct 2020

Funding

Z.W. and Y.D. acknowledge support from the China Scholarship Council (CSC). C.S. acknowledges the European Union for a Marie Curie European Postdoctoral Fellowship (FlowAct, Grant 794072). G.L. acknowledges financial support from the Dutch Science Foundation (NWO) for a VIDI Grant for T.N. (SensPhotoFlow, 14150). Finally, the authors acknowledge support from COST Action CA15106 (C–H Activation in Organic Synthesis, CHAOS). We thank Creaflow and Ajinomoto Bio-Pharma Services for the use of the HANU reactor and the irradiation source.

Funders	Funder number
European Union's Horizon 2020 - Research and Innovation Framework Programme	794072
European Commission
European Cooperation in Science and Technology (COST)	CA15106
Nederlandse Organisatie voor Wetenschappelijk Onderzoek	14150
China Scholarship Council

Keywords

C-H functionalization
decatungstate
flow photochemistry
hydrogen atom transfer
photocatalysis
process intensification

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10.1021/acs.oprd.0c00235

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title = "Optimization of a Decatungstate-Catalyzed C(sp3)–H Alkylation Using a Continuous Oscillatory Millistructured Photoreactor",

abstract = "Tetrabutylammonium decatungstate (TBADT) has emerged as an efficient and versatile photocatalyst for hydrogen atom transfer (HAT) processes that enables the cleavage of both activated and unactivated aliphatic C–H bonds. Using a recently developed oscillatory millistructured continuous-flow photoreactor, investigations of a decatungstate-catalyzed C(sp3)–H alkylation protocol were carried out, and the results are presented here. The performance of the reactor was evaluated in correlation to several chemical and process parameters, including residence time, light intensity, catalyst loading, and substrate/reagent concentration. In comparison with previously reported batch and flow protocols, conditions were found that led to considerably higher productivity, achieving a throughput up to 36.7 mmol/h with a residence time of only 7.5 min.",

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AU - Wen, Zhenghui

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AU - Sambiagio, Carlo

AU - Deng, Yuchao

AU - Laudadio, Gabriele

AU - Van Aken, Koen

AU - Sun, Yuhan

AU - Gemoets, H.P.L.

AU - Noël, Timothy

PY - 2020/10/16

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N2 - Tetrabutylammonium decatungstate (TBADT) has emerged as an efficient and versatile photocatalyst for hydrogen atom transfer (HAT) processes that enables the cleavage of both activated and unactivated aliphatic C–H bonds. Using a recently developed oscillatory millistructured continuous-flow photoreactor, investigations of a decatungstate-catalyzed C(sp3)–H alkylation protocol were carried out, and the results are presented here. The performance of the reactor was evaluated in correlation to several chemical and process parameters, including residence time, light intensity, catalyst loading, and substrate/reagent concentration. In comparison with previously reported batch and flow protocols, conditions were found that led to considerably higher productivity, achieving a throughput up to 36.7 mmol/h with a residence time of only 7.5 min.

AB - Tetrabutylammonium decatungstate (TBADT) has emerged as an efficient and versatile photocatalyst for hydrogen atom transfer (HAT) processes that enables the cleavage of both activated and unactivated aliphatic C–H bonds. Using a recently developed oscillatory millistructured continuous-flow photoreactor, investigations of a decatungstate-catalyzed C(sp3)–H alkylation protocol were carried out, and the results are presented here. The performance of the reactor was evaluated in correlation to several chemical and process parameters, including residence time, light intensity, catalyst loading, and substrate/reagent concentration. In comparison with previously reported batch and flow protocols, conditions were found that led to considerably higher productivity, achieving a throughput up to 36.7 mmol/h with a residence time of only 7.5 min.

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Optimization of a Decatungstate-Catalyzed C(sp3)–H Alkylation Using a Continuous Oscillatory Millistructured Photoreactor

Abstract

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Supplementary data for the paper: Optimization of a decatungstate-catalyzed C(sp³)-H alkylation using a continuous oscillatory milli-structured photoreactor

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Optimization of a Decatungstate-Catalyzed C(sp3)–H Alkylation Using a Continuous Oscillatory Millistructured Photoreactor

Abstract

Funding

Keywords

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Datasets

Supplementary data for the paper: Optimization of a decatungstate-catalyzed C(sp³)-H alkylation using a continuous oscillatory milli-structured photoreactor

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