Catalytic methods for peroxide mediated oxidation
Lead Research Organisation:
University of Strathclyde
Department Name: Pure and Applied Chemistry
Abstract
The project will involve development of synthetic methodology guided by mechanistic insight of importance to the thematic areas of Healthcare Technologies, Physical Sciences and Manufacturing the Future.
We have recently reported a metal-free method for the dihydroxylation of alkenes that proceeds in the presence of both moisture and air (J. Am. Chem. Soc. 2010, 132, 14409). Treatment of an alkene with one equivalent of a malonoyl peroxide (CHCl3; 0.5 M; r.t.; H2O 1 equiv), followed by hydrolysis, gives the corresponding diol in 82-96% isolated yield with syn selectivity (up to 50:1). This represents an effective method for the dihydroxylation of alkenes which has significant advantages over traditional transition-metal catalysed processes and has great potential for development. In order to realise the full potential of this protocol a catalytic procedure must be developed. We therefore wish to undertake a project with the following major goals and objectives:
* Develop a novel catalytic cycle for the dihydroxylation of alkenes.
* Establish the scope of the process for substituted alkenes.
* Characterise the kinetics and mechanism of the catalytic cycle.
Successful outcome of this project will deliver a simple, effective and industry relevant catalytic oxidation procedure that proceeds at room temperature in the presence of moisture and air.
We have recently reported a metal-free method for the dihydroxylation of alkenes that proceeds in the presence of both moisture and air (J. Am. Chem. Soc. 2010, 132, 14409). Treatment of an alkene with one equivalent of a malonoyl peroxide (CHCl3; 0.5 M; r.t.; H2O 1 equiv), followed by hydrolysis, gives the corresponding diol in 82-96% isolated yield with syn selectivity (up to 50:1). This represents an effective method for the dihydroxylation of alkenes which has significant advantages over traditional transition-metal catalysed processes and has great potential for development. In order to realise the full potential of this protocol a catalytic procedure must be developed. We therefore wish to undertake a project with the following major goals and objectives:
* Develop a novel catalytic cycle for the dihydroxylation of alkenes.
* Establish the scope of the process for substituted alkenes.
* Characterise the kinetics and mechanism of the catalytic cycle.
Successful outcome of this project will deliver a simple, effective and industry relevant catalytic oxidation procedure that proceeds at room temperature in the presence of moisture and air.
People |
ORCID iD |
| Nicholas Tomkinson (Primary Supervisor) | |
| Jonathan Curle (Student) |
Studentship Projects
| Project Reference | Relationship | Related To | Start | End | Student Name |
|---|---|---|---|---|---|
| EP/N509371/1 | 01/10/2015 | 31/01/2022 | |||
| 1811694 | Studentship | EP/N509371/1 | 01/10/2016 | 30/09/2020 | Jonathan Curle |
| Description | Many key reactions within chemistry use highly toxic and rare metals. It is therefore important to develop alternative chemical reactions that avoid such metals. The aim of my research is to develop such a procedure, that is metal-free and therefore more eco-friendly. Specifically we are looking at the oxyamination reaction, whereby we install a nitrogen and oxygen atom across an alkene double bond. This has already been achieved previously by different research groups, however most procedures found within the literature use hypervalent iodine reagents and often have poor atom efficiency. Within this project we have develop the first intermolecular oxyamination procedure using a malonoyl peroxide. This reagent is non-toxic, relatively cheap and has a better atom efficiency than procedures already in the literature. This research has now successfully been published. |
| Exploitation Route | Work carried out will be carried forward by the next intake of PhD students. |
| Sectors | Chemicals,Environment |
| URL | https://pubs.acs.org/doi/abs/10.1021/acs.orglett.0c00253 |