Cardiff University | Prifysgol Caerdydd ORCA
Online Research @ Cardiff 
WelshClear Cookie - decide language by browser settings

Diazo compounds in continuous flow technology

Mueller, Simon T. R. 2015. Diazo compounds in continuous flow technology. PhD Thesis, Cardiff University.
Item availability restricted.

[thumbnail of Simon Mueller Thesis_corrected_10022016 SIGS REMOVED.pdf]
Preview
PDF - Accepted Post-Print Version
Available under License Creative Commons Attribution Non-commercial No Derivatives.

Download (9MB) | Preview
[thumbnail of Simon Mueller form.pdf] PDF - Supplemental Material
Restricted to Repository staff only

Download (634kB)

Abstract

Diazo compounds are highly reactive carbene precursors which can be used to generate molecular complexity rapidly. However, diazo compounds are highly energetic and dangerous compounds and therefore, their use in large-scale applications remains rare. In this work, the use of continuous flow technology for the safe, efficient and scalable use of diazo compounds is described. By using flow chemistry, diazo compounds were safely generated within small diameter devices and directly used in subsequent reactions without a hazardous isolation of the diazo reagents. This thesis describes five new protocols for the use of diazo compounds. In the first project, ethyl diazoacetate (EDA) was generated safely in flow and used in subsequent aldol addition reactions to aldehydes with high yields (right). The preparation of the organometallic ethyl lithiodiazoacetate species in flow was achieved in the second project and used for the addition to ketones (left). Detailed kinetic and thermal studies on aryl diazoacetates were performed in the third project which yielded a new, multistep continuous flow protocol for the use of donor / acceptor carbenes. Rapid reaction optimisation was achieved using in-line infrared spectroscopy. Purification of the diazo species was performed in flow using in-line liquid / liquid extraction methodology. The fourth protocol entails the rapid assembly of complex lactone-cyclopropane structures of biological interest from diazo compounds in a combination of flow and batch technologies (left). In the final project, the stereoselective preparation of indolines using diazo compounds is discussed (right).

Item Type: Thesis (PhD)
Date Type: Completion
Status: Unpublished
Schools: Chemistry
Subjects: Q Science > QD Chemistry
Date of First Compliant Deposit: 30 March 2016
Last Modified: 17 Jan 2024 16:19
URI: https://orca.cardiff.ac.uk/id/eprint/86662

Actions (repository staff only)

Edit Item Edit Item

Downloads

Downloads per month over past year

View more statistics