eprintid: 1309819
rev_number: 15
eprint_status: archive
userid: 602
dir: disk0/01/30/98/19
datestamp: 2011-08-09 16:28:51
lastmod: 2015-07-20 18:44:24
status_changed: 2011-08-09 16:28:51
type: thesis
metadata_visibility: show
item_issues_count: 0
creators_name: Ahern, J.M.
title: Radical hydroacylation of C-C and N-N double bonds in air
ispublished: unpub
divisions: F56
abstract: The formation of C-C and C-N bonds in modern organic synthesis is a key target for
methodological advancement. Current methods of C-C and C-N bond formation
often involve the use of expensive catalysts, or sub-stoichiometric reagents, which
can lead to the generation of undesirable waste products. This thesis describes a
novel and environmentally benign set of reaction conditions for the formation of C-C
and C-N bonds by hydroacylation and this is promoted by mixing two reagents, an
aldehyde and an electron-deficient double bond, under freely available atmospheric
oxygen at room temperature
Chapter 1 will provide an introduction to the thesis and mainly discusses methods for
C-C bond formation, in particular, radical chemistry and hydroacylation. Chapter 2
describes the hydroacylation of vinyl sulfonates and vinyl sulfones (C-C double
bonds) with aliphatic and aromatic aldehydes with a discussion and evidence for the
mechanism of the transformation. Chapter 3 details the synthesis of precursors for
intramolecular cyclisations and studies into aerobic intramolecular cyclisations.
Chapter 4 describes the hydroacylation of vinyl phosphonates (C-C double bonds)
and diazocarboxylates (N-N double bonds) with aliphatic and aromatic aldehydes
bearing functional groups. In addition, the hydroacylation of diazocarboxylates with
chiral aldehydes will be discussed.
In conclusion, a new, facile and clean set of reaction conditions for the formation of
C-C and C-N bonds has been developed via aerobic C-H activation of aldehydes
providing access to unsymmetrical ketones.
date: 2011-04-28
vfaculties: VMPS
oa_status: green
thesis_class: doctoral_open
language: eng
thesis_view: UCL_Thesis
dart: DART-Europe
primo: open
primo_central: open_green
full_text_status: public
pages: 135
institution: UCL (University College London)
department: Department of Chemistry
thesis_type: Doctoral
citation:        Ahern, J.M.;      (2011)    Radical hydroacylation of C-C and N-N double bonds in air.                   Doctoral thesis , UCL (University College London).     Green open access   
 
document_url: https://discovery.ucl.ac.uk/id/eprint/1309819/1/1309819.pdf