Radical hydroacylation of C-C and N-N double bonds in air
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. T...
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ndltd-bl.uk-oai-ethos.bl.uk-5652652015-12-03T03:27:07ZRadical hydroacylation of C-C and N-N double bonds in airAhern, J. M.2011The 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.540University College London (University of London)http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.565265http://discovery.ucl.ac.uk/1309819/Electronic Thesis or Dissertation |
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540 Ahern, J. M. Radical hydroacylation of C-C and N-N double bonds in air |
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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. |
author |
Ahern, J. M. |
author_facet |
Ahern, J. M. |
author_sort |
Ahern, J. M. |
title |
Radical hydroacylation of C-C and N-N double bonds in air |
title_short |
Radical hydroacylation of C-C and N-N double bonds in air |
title_full |
Radical hydroacylation of C-C and N-N double bonds in air |
title_fullStr |
Radical hydroacylation of C-C and N-N double bonds in air |
title_full_unstemmed |
Radical hydroacylation of C-C and N-N double bonds in air |
title_sort |
radical hydroacylation of c-c and n-n double bonds in air |
publisher |
University College London (University of London) |
publishDate |
2011 |
url |
http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.565265 |
work_keys_str_mv |
AT ahernjm radicalhydroacylationofccandnndoublebondsinair |
_version_ |
1718141075360579584 |