Continuous flow epoxidation of alkenes using a homogeneous manganese catalyst with peracetic acid

Ailbhe A. Ryan; Seán D. Dempsey; Megan Smyth; Karen Fahey; Thomas S. Moody; Scott Wharry; Paul Dingwall; David W. Rooney; Jillian M. Thompson; Peter C. Knipe; Mark J. Muldoon

doi:10.1021/acs.oprd.2c00222

Continuous flow epoxidation of alkenes using a homogeneous manganese catalyst with peracetic acid

Ailbhe A. Ryan, Seán D. Dempsey, Megan Smyth, Karen Fahey, Thomas S. Moody, Scott Wharry, Paul Dingwall, David W. Rooney, Jillian M. Thompson^*, Peter C. Knipe^*, Mark J. Muldoon^*

^*Corresponding author for this work

School of Chemistry and Chemical Engineering

Research output: Contribution to journal › Article › peer-review

9 Citations (Scopus)

97 Downloads (Pure)

Abstract

Epoxidation of alkenes is a valuable transformation in the synthesis of fine chemicals. Described herein are the design and development of a continuous flow process for carrying out the epoxidation of alkenes with a homogeneous manganese catalyst at metal loadings as low as 0.05 mol%. In this process, peracetic acid is generated in situ and telescoped directly into the epoxidation reaction, thus reducing the risks associated with its handling and storage, which often limit its use at scale. This flow process lessens the safety hazards associated with both the exothermicity of this epoxidation reaction and the use of the highly reactive peracetic acid. Controlling the speciation of manganese/2-picolinic acid mixtures by varying the ligand:manganese ratio was key to the success of the reaction. This continuous flow process offers an inexpensive, sustainable, and scalable route to epoxides.

Original language	English
Pages (from-to)	262-268
Number of pages	7
Journal	Organic Process Research & Development
Volume	27
Issue number	2
Early online date	14 Jan 2023
DOIs	https://doi.org/10.1021/acs.oprd.2c00222
Publication status	Published - 17 Feb 2023

Keywords

catalysis
continuous processing
epoxidation
flow chemistry
manganese
oxidation

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry

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10.1021/acs.oprd.2c00222Licence: CC BY

Continuous flow epoxidation of alkenes using a homogeneous manganese catalyst with peracetic acid
Copyright 2023 The Authors. This is an open access article published under a Creative Commons Attribution License (https://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.
Final published version, 1.42 MBLicence: CC BY

The development of continuous flow systems for manganese catalysed oxidation reactions
Ryan, A. (Author), Knipe, P. (Supervisor), Dingwall, P. (Supervisor) & Muldoon, M. (Supervisor), Dec 2023
Student thesis: Doctoral Thesis › Doctor of Philosophy

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title = "Continuous flow epoxidation of alkenes using a homogeneous manganese catalyst with peracetic acid",

abstract = "Epoxidation of alkenes is a valuable transformation in the synthesis of fine chemicals. Described herein are the design and development of a continuous flow process for carrying out the epoxidation of alkenes with a homogeneous manganese catalyst at metal loadings as low as 0.05 mol%. In this process, peracetic acid is generated in situ and telescoped directly into the epoxidation reaction, thus reducing the risks associated with its handling and storage, which often limit its use at scale. This flow process lessens the safety hazards associated with both the exothermicity of this epoxidation reaction and the use of the highly reactive peracetic acid. Controlling the speciation of manganese/2-picolinic acid mixtures by varying the ligand:manganese ratio was key to the success of the reaction. This continuous flow process offers an inexpensive, sustainable, and scalable route to epoxides.",

keywords = "catalysis, continuous processing, epoxidation, flow chemistry, manganese, oxidation",

author = "Ryan, {Ailbhe A.} and Dempsey, {Se{\'a}n D.} and Megan Smyth and Karen Fahey and Moody, {Thomas S.} and Scott Wharry and Paul Dingwall and Rooney, {David W.} and Thompson, {Jillian M.} and Knipe, {Peter C.} and Muldoon, {Mark J.}",

year = "2023",

month = feb,

day = "17",

doi = "10.1021/acs.oprd.2c00222",

language = "English",

volume = "27",

pages = "262--268",

journal = "Organic Process Research & Development",

issn = "1083-6160",

publisher = "American Chemical Society",

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TY - JOUR

T1 - Continuous flow epoxidation of alkenes using a homogeneous manganese catalyst with peracetic acid

AU - Ryan, Ailbhe A.

AU - Dempsey, Seán D.

AU - Smyth, Megan

AU - Fahey, Karen

AU - Moody, Thomas S.

AU - Wharry, Scott

AU - Dingwall, Paul

AU - Rooney, David W.

AU - Thompson, Jillian M.

AU - Knipe, Peter C.

AU - Muldoon, Mark J.

PY - 2023/2/17

Y1 - 2023/2/17

N2 - Epoxidation of alkenes is a valuable transformation in the synthesis of fine chemicals. Described herein are the design and development of a continuous flow process for carrying out the epoxidation of alkenes with a homogeneous manganese catalyst at metal loadings as low as 0.05 mol%. In this process, peracetic acid is generated in situ and telescoped directly into the epoxidation reaction, thus reducing the risks associated with its handling and storage, which often limit its use at scale. This flow process lessens the safety hazards associated with both the exothermicity of this epoxidation reaction and the use of the highly reactive peracetic acid. Controlling the speciation of manganese/2-picolinic acid mixtures by varying the ligand:manganese ratio was key to the success of the reaction. This continuous flow process offers an inexpensive, sustainable, and scalable route to epoxides.

AB - Epoxidation of alkenes is a valuable transformation in the synthesis of fine chemicals. Described herein are the design and development of a continuous flow process for carrying out the epoxidation of alkenes with a homogeneous manganese catalyst at metal loadings as low as 0.05 mol%. In this process, peracetic acid is generated in situ and telescoped directly into the epoxidation reaction, thus reducing the risks associated with its handling and storage, which often limit its use at scale. This flow process lessens the safety hazards associated with both the exothermicity of this epoxidation reaction and the use of the highly reactive peracetic acid. Controlling the speciation of manganese/2-picolinic acid mixtures by varying the ligand:manganese ratio was key to the success of the reaction. This continuous flow process offers an inexpensive, sustainable, and scalable route to epoxides.

KW - catalysis

KW - continuous processing

KW - epoxidation

KW - flow chemistry

KW - manganese

KW - oxidation

U2 - 10.1021/acs.oprd.2c00222

DO - 10.1021/acs.oprd.2c00222

M3 - Article

AN - SCOPUS:85146620107

SN - 1083-6160

VL - 27

SP - 262

EP - 268

JO - Organic Process Research & Development

JF - Organic Process Research & Development

IS - 2

ER -

Continuous flow epoxidation of alkenes using a homogeneous manganese catalyst with peracetic acid

Abstract

Keywords

ASJC Scopus subject areas

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Student theses

The development of continuous flow systems for manganese catalysed oxidation reactions

Cite this