TY  - UNPB
ID  - discovery1309819
N2  - 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.
UR  - https://discovery.ucl.ac.uk/id/eprint/1309819/
PB  - UCL (University College London)
M1  - Doctoral
A1  - Ahern, J.M.
TI  - Radical hydroacylation of C-C and N-N double bonds in air
EP  - 135
Y1  - 2011/04/28/
AV  - public
N1  - Unpublished
ER  -