Research areas

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Dr. Andrew Clark Associate Professor in Synthetic
Chemistry
Research areas
Natural product isolation and total synthesis.
Chemistry and biology of free radicals
Development of synthetic methodology using
copper, iron and ruthenium
Functional Genomics / Chemical Genetics /
Interactomics
Use of plants in renewable plastics manufacture
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Recent Developments in Heterocycle Synthesis via
Atom Transfer Radical Cyclisation
Dr. Andrew Clark Chemistry Department, University
of Warwick Coventry, UK 44 24 76523242 msrir_at_csv.
warwick.ac.uk
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Atom Transfer Radical Cyclisation
H. Nagashima et al, Tetrahedron Lett., 1983, 24,
2395 A. J. Clark, Chem. Soc. Rev., 2002, 31, 1
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H. Nagashima et al, J. Org. Chem., 1993, 58, 464
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A. J. Clark, D. Duncalf, R. P. Filik, D. M.
Haddleton, G. H. Thomas, H. Wongtap, Tet. Letts,
1999, 40, 3807
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Steric Effect of N-Substituent
de 54
de 44
de 2
de 34
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Relative rate versus ligand equivalence
Toluene
A. J. Clark, F. De Campo, R. J. Deeth, R. P.
Filik, S. Gatard, N. A. Hunt, D. Lastecoueres,
G. H. Thomas, J-B. Verlhac, H. Wongtap, J. Chem.
Soc., Perkin 1, 2000, 671
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D. M. Haddleton, D. J. Duncalf, D. Kukulj, M. C.
Crossman, S. G. Jackson, S. A. F. Bon, A. J.
Clark, A. J. Shooter, Eur. J. Inorg. Chem. 1998,
1799
D. M. Haddleton, A. J. Clark, D. J. Duncalf, A.
M. Heming, D. Kukulj, A. J. Shooter , J.
Chem.Soc., Dalton Trans, 1998, 381
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A. J. Clark, F. De Campo, R. J. Deeth, R. P.
Filik, S. Gatard, N. A. Hunt, D. Lastecoueres,
G. H. Thomas, J-B. Verlhac, H. Wongtap, J. Chem.
Soc., Perkin 1, 2000, 671
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A. J. Clark, J. V. Geden, and S. Thom. J. Org.
Chem., 2006, 71, 1471
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Ligand Acceleration
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Solid Supported Catalysts for ATRC
A. J. Clark et al, J. Org. Chem., 1999, 64, 8954
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Kinetics to 80 Conversion (PS-PMDETA.CuCl)
Ln(Ao/A)
Time (hrs)
A. J. Clark, J. V. Geden, and S. Thom. J. Org.
Chem., 2006, 71, 1471
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F. Ghelfi et al, Tetrahedron., 1997, 41, 1403
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A. J. Clark, G. M. Battle, A. Bridge, Tet.
Letts., 2001, 42, 1999.
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A. J. Clark, C. P. Dell, J. M. Ellard, N. A.
Hunt, J. P. McDonagh, Tet. Letts., 1999, 40, 8619
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A. J. Clark, C. P. Dell, J. M. Ellard, N. A.
Hunt, J. P. McDonagh, Tet. Letts., 1999, 40, 8619
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A. J. Clark, C. P. Dell, J. P. McDonagh, C. R.
Acad. Sci. Ser IIc Chim, 2001, 4, 575
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Application to natural product synthesis
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A. J. Clark, J. V. Geden, S. Thom, J. Org. Chem.,
2006, in preparation
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A. J. Clark, G.M. Battle, A. Bridge, Tetrahedron
Letts., 2001, 42, 4409
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A. J. Clark, C. P. Dell, J. M. McDonagh, J.
Geden, P. Mawdsley, Org. Letts., 2003, 5, 2063
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Cyclisation in ionic liquids
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Further Application of Solid Supported Catalysts
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Unhindered phenols
Control
Ortho substituted hindered phenol
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A. J. Clark, M. C. Crossman, D.Duncalf, D. M.
Haddleton,S. R. Morsley, A. J.Shooter, J.
Chem.Soc., Chem Commun., 1997, 1734
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Catalyst complex in water 25C (Cu ligand 1
3)
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Catalyst Complex in water at 50C
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5-Exo Cyclisation
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• Five cyclisation products isolated 6-endo (A
  and B) and 5-exo (C, D and E)
• Ratio A B C D E 6.5 4.5 4.5 1.8
  1.0 (crude 1H NMR)
• NMR experiments have confirmed relative
  stereochemistry of C and D
• Ratio 6-endo 5-exo 1.5 1 (crude 1H NMR)
  2 1 (isolated)

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6-Endo Cyclisation
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6-Endo Cyclisation
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Cyclisation in ionic liquids
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A. J. Clark, M. C. Crossman, D.Duncalf, D. M.
Haddleton,S. R. Morsley, A. J.Shooter, J.
Chem.Soc., Chem Commun., 1997, 1734
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Catalyst complex in water 25C (Cu ligand 1
3)
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Catalyst Complex in water at 50C
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