Daisy-Chaining Photo- and Thermal Chemistry: Multi-Step Continuous Flow Synthesis of Visible-Light Mediated Photo-chemistry with a High Temperature Cascade Reaction

Luke D Elliott; Kevin I Booker-Milburn; Alastair J J Lennox

doi:10.1021/acs.oprd.1c00187

Daisy-Chaining Photo- and Thermal Chemistry: Multi-Step Continuous Flow Synthesis of Visible-Light Mediated Photo-chemistry with a High Temperature Cascade Reaction

Luke D Elliott, Kevin I Booker-Milburn, Alastair J J Lennox^*

^*Corresponding author for this work

Research output: Contribution to journal › Article (Academic Journal) › peer-review

Abstract

A highly efficient visible light mediated photochemical [2+2] cycloaddition is coupled with an atom economic thermal cascade reaction in a continuous flow process. By moving the photochemistry from UV to visible it is made more energy efficient and can be conducted with readily available equipment. The application of high-temperature flow chemistry to the thermal cascade step allows for safe and reliable scale-up with short reaction times. Thus, we demonstrate a rare example of a photo/thermal daisy-chained process and, specifically, the first visible light mediated excited state to thermal cascade reaction as a fully continuous process (20 g/h). The synthetic utility of flow chemistry is further showcased by the isolation of a reactive intermediate at quantities not possible under batch conditions.

Original language	English
Pages (from-to)	1943-1949
Number of pages	7
Journal	Organic Process Research & Development
Volume	25
Issue number	8
Early online date	19 Jul 2021
DOIs	https://doi.org/10.1021/acs.oprd.1c00187
Publication status	Published - 20 Aug 2021

Bibliographical note

Funding Information:
We thank the EPSRC (EP/P013341/1 and EP/S018050/1) and the Royal Society (University Research Fellowship to AJJL) for funding, Steve Evans and Mark Ladlow (Uniqsis) for the loan of the FlowSyn and PhotoSyn reactors, and Paul Dinham and Paul Chappell (University of Bristol) for reactor construction.

Publisher Copyright:
© 2021 American Chemical Society.

Keywords

cascade
photochemistry
visible light
flow
Diels-Alder
rearrangement

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10.1021/acs.oprd.1c00187

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Cite this

@article{8ea9c8aebbb94837b2dce1924a3e0a65,

title = "Daisy-Chaining Photo- and Thermal Chemistry: Multi-Step Continuous Flow Synthesis of Visible-Light Mediated Photo-chemistry with a High Temperature Cascade Reaction",

abstract = "A highly efficient visible light mediated photochemical [2+2] cycloaddition is coupled with an atom economic thermal cascade reaction in a continuous flow process. By moving the photochemistry from UV to visible it is made more energy efficient and can be conducted with readily available equipment. The application of high-temperature flow chemistry to the thermal cascade step allows for safe and reliable scale-up with short reaction times. Thus, we demonstrate a rare example of a photo/thermal daisy-chained process and, specifically, the first visible light mediated excited state to thermal cascade reaction as a fully continuous process (20 g/h). The synthetic utility of flow chemistry is further showcased by the isolation of a reactive intermediate at quantities not possible under batch conditions.",

keywords = "cascade, photochemistry, visible light, flow, Diels-Alder, rearrangement",

author = "Elliott, {Luke D} and Booker-Milburn, {Kevin I} and Lennox, {Alastair J J}",

note = "Funding Information: We thank the EPSRC (EP/P013341/1 and EP/S018050/1) and the Royal Society (University Research Fellowship to AJJL) for funding, Steve Evans and Mark Ladlow (Uniqsis) for the loan of the FlowSyn and PhotoSyn reactors, and Paul Dinham and Paul Chappell (University of Bristol) for reactor construction. Publisher Copyright: {\textcopyright} 2021 American Chemical Society.",

year = "2021",

month = aug,

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doi = "10.1021/acs.oprd.1c00187",

language = "English",

volume = "25",

pages = "1943--1949",

journal = "Organic Process Research & Development",

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publisher = "American Chemical Society",

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Daisy-Chaining Photo- and Thermal Chemistry : Multi-Step Continuous Flow Synthesis of Visible-Light Mediated Photo-chemistry with a High Temperature Cascade Reaction. / Elliott, Luke D; Booker-Milburn, Kevin I; Lennox, Alastair J J.

In: Organic Process Research & Development, Vol. 25, No. 8, 20.08.2021, p. 1943-1949.

Research output: Contribution to journal › Article (Academic Journal) › peer-review

TY - JOUR

T1 - Daisy-Chaining Photo- and Thermal Chemistry

T2 - Multi-Step Continuous Flow Synthesis of Visible-Light Mediated Photo-chemistry with a High Temperature Cascade Reaction

AU - Elliott, Luke D

AU - Booker-Milburn, Kevin I

AU - Lennox, Alastair J J

N1 - Funding Information: We thank the EPSRC (EP/P013341/1 and EP/S018050/1) and the Royal Society (University Research Fellowship to AJJL) for funding, Steve Evans and Mark Ladlow (Uniqsis) for the loan of the FlowSyn and PhotoSyn reactors, and Paul Dinham and Paul Chappell (University of Bristol) for reactor construction. Publisher Copyright: © 2021 American Chemical Society.

PY - 2021/8/20

Y1 - 2021/8/20

N2 - A highly efficient visible light mediated photochemical [2+2] cycloaddition is coupled with an atom economic thermal cascade reaction in a continuous flow process. By moving the photochemistry from UV to visible it is made more energy efficient and can be conducted with readily available equipment. The application of high-temperature flow chemistry to the thermal cascade step allows for safe and reliable scale-up with short reaction times. Thus, we demonstrate a rare example of a photo/thermal daisy-chained process and, specifically, the first visible light mediated excited state to thermal cascade reaction as a fully continuous process (20 g/h). The synthetic utility of flow chemistry is further showcased by the isolation of a reactive intermediate at quantities not possible under batch conditions.

AB - A highly efficient visible light mediated photochemical [2+2] cycloaddition is coupled with an atom economic thermal cascade reaction in a continuous flow process. By moving the photochemistry from UV to visible it is made more energy efficient and can be conducted with readily available equipment. The application of high-temperature flow chemistry to the thermal cascade step allows for safe and reliable scale-up with short reaction times. Thus, we demonstrate a rare example of a photo/thermal daisy-chained process and, specifically, the first visible light mediated excited state to thermal cascade reaction as a fully continuous process (20 g/h). The synthetic utility of flow chemistry is further showcased by the isolation of a reactive intermediate at quantities not possible under batch conditions.

KW - cascade

KW - photochemistry

KW - visible light

KW - flow

KW - Diels-Alder

KW - rearrangement

U2 - 10.1021/acs.oprd.1c00187

DO - 10.1021/acs.oprd.1c00187

M3 - Article (Academic Journal)

VL - 25

SP - 1943

EP - 1949

JO - Organic Process Research & Development

JF - Organic Process Research & Development

SN - 1083-6160

IS - 8

ER -

Daisy-Chaining Photo- and Thermal Chemistry: Multi-Step Continuous Flow Synthesis of Visible-Light Mediated Photo-chemistry with a High Temperature Cascade Reaction

Abstract

Bibliographical note

Keywords

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