We thank EPSRC, King's College London, and University of Birmingham for funding (DTA studentship to E.J.W.). R.S.G. thanks EPSRC for the award of an Advanced Research Fellowship (2005–2010). We additionally thank Dr. Andreas E. Goeta (Durham University) for X-ray crystallography, Dr. Neil Spencer (University of Birmingham) for NMR experiments, and Graham Burns (University of Birmingham) for HPLC analysis.
1521-3773/asset/2002_left.gif?v=1&s=ac6b0d94a94d7ce7a210002b8096b42feffc0bcf)
1521-3773/asset/2002_right.gif?v=1&s=451042aa3415ae3ad0729984d26dee1866aca82e)
Communication
Formal Synthesis of (−)-Aphanorphine Using Sequential Photomediated Radical Reactions of Dithiocarbamates†
Article first published online: 6 JUN 2007
DOI: 10.1002/anie.200701055
Copyright © 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Additional Information
How to Cite
Grainger, R. and Welsh, E. (2007), Formal Synthesis of (−)-Aphanorphine Using Sequential Photomediated Radical Reactions of Dithiocarbamates. Angewandte Chemie International Edition, 46: 5377–5380. doi: 10.1002/anie.200701055
- †
Publication History
- Issue published online: 2 JUL 2007
- Article first published online: 6 JUN 2007
- Manuscript Received: 9 MAR 2007
Funded by
- EPSRC
- King's College London
Keywords:
- cyclization;
- metathesis;
- oxidation;
- radical reactions;
- sulfinamides
Graphical Abstract
Time to change the light bulb: An alkyl dithiocarbamate, itself formed through a photoinitiated group-transfer cyclization of a carbamoyl radical, undergoes a second photomediated radical process initiated with a different light source. These two reactions, which proceed through the same cyclohexenyl radical intermediate, are key steps in a new asymmetric synthesis of the alkaloid aphanorphine. TEMPO=2,2,6,6-tetramethyl-1-piperidinoxyl radical.