Greener Organic Methodology and Homogeneous Catalysis

Matt Clarke

 

This webpage is getting redeveloped.

Since you might be looking for some information about my group’s research, here is my publication list.

 

Matt Clarke: I direct a research group interested in greener and scalable synthetic methods for the production of pharmaceutical intermediates and specialty chemicals. This involves the study of both homogeneous (metal and organo) catalysts, and heterogeneous catalysts (MOFs). A core interest is in catalytic carbonylation reactions. The group’s discoveries have been recognized with several research prizes and fellowships.

 

 

 

Matt Clarke: Publications (1999-summer 2015)

 

  1. 1. First highly enantioselective allylic alkylations catalysed by platinum complexes.  A.J. Blacker, M. L. Clarke (listed in the paper as Clark),  M. S. Loft and J.M.J. Williams.  J. Chem. Soc. Chem. Commun., 1999, 913. 

  2. 2. Synthesis and structure of enantiomerically pure platinum complexes of phosphino-oxazolines and their use in asymmetric catalysis.  A. J. Blacker, M. L. Clarke,  M. S. Loft, M. F. Mahon and J.M.J. Williams.  Organometallics, 1999, 18, 2867.  

  3. 3. Use of Tricyclohexylphosphine to control regioselectivity in palladium catalysed allylic alkylations. A.J. Blacker, M.L.Clarke,  M.S. Loft and J.M.J. Williams, Org. Lett. 1999, 1, 1969. 

  4. 4.  Platinum catalysed allylic alkylation: Reactivity, regioselectivity and enantioselectivity.  A. J. Blacker, M. L. Clarke, M. S. Humphries, M. S. Loft,  M.F. Mahon and J.M.J. Williams.  Chemistry: A Euro. Journal, 2000, 6, 353. 

  5. 5. The synthesis and applications of phosphines. M. L. Clarke and J. M. J. Williams, chap.2 in Organophosphorus Chemistry:  A Practical approach.  Ed. P.J. Murphy, OUP, Oxford, 2004. 

  6. 6. P-N bond formation as a route to highly electron rich phosphine ligands.  M. L. Clarke, D. J. Cole-Hamilton, A. M. Z. Slawin, and J. D. Woollins, J. Chem. Soc. Chem. Commun., 2000, 2065.  

  7. 7. Recent advances in homogenous catalysis using platinum complexes.  M. L. Clarke, Polyhedron, 2001, 20, 151. 

  8. 8. Synthesis, structure, and co-ordination behaviour of a novel multifunctionalised diphosphine containing a P-N-Si-N-P backbone.  M. L. Clarke, D. J. Cole-Hamilton, A. M. Z. Slawin, and J. D. Woollins, J. Chem. Soc. Dalton Trans., 2001, 972. 

  9. 9. First examples of M-Se-P-N-N heterocycles.  M. L. Clarke, G. L. Holliday, A. M. Z. Slawin and J. D. Woollins, Inorg. Chem. Commun., 2001, 4, 115. 

  10. 10. P-N bond formation as a route to a highly electron rich bidentate phosphine ligand and its use in hydroformylation of olefins.  M. Rodriguez i Zubiri, M. L. Clarke, D. J. Cole-Hamilton, A. M. Z. Slawin, and J. D. Woollins, J. Chem. Soc. Dalton Trans., 2001, 969. 

  11. 11. Rhodium complexes derived from amine functionalised phosphines.  M. L. Clarke, A. M. Z. Slawin, M. Wheatley and J. D. Woollins.  J. Chem. Soc. Dalton Trans., 2001, 3421.  

  12. 12. Synthesis of bulky, electron rich hemilabile phosphines and their application in the Suzuki reaction of aryl chlorides.  M. L. Clarke, D. J. Cole-Hamilton, and J. D. Woollins, J. Chem. Soc. Dalton Trans., 2001, 2721.  

  13. 13. Electron rich alkyl- and dialkyl- pyrrolidinylphosphines:  An evaluation of their electronic, steric, and catalytic properties.  M. L. Clarke, D. J. Cole-Hamilton, A.M.Z. Slawin, and J. D. Woollins, J. Chem. Soc. Dalton Trans., 2002, 1093.  

  14. 14. Co-ordination chemistry and metal catalysed carbonylation reactions using  8-(diphenylphosphinomethyl)aminoquinoline:  A ligand that displays mono-, bi-, and tri-dentate co-ordination modes.  M. L. Clarke, D. J. Cole-Hamilton, D. F. Foster, A. M. Z. Slawin and J. D. Woollins, J. Chem. Soc., Dalton Trans., 2002, 1624. 

  15. 15. Synthesis and co-ordination chemistry of Ph2P(CH2)nNHP iPr2. T. Appleby, S. M. Aucott, M. L. Clarke, A. M. Z. Slawin, and J. D. Woollins, Polyhedron, 2002, 2639. 

  16. 16. Platinum complexes derived from tertiary amine functionalised phosphines.  M. L. Clarke, A. M. Z. Slawin, and J. D. Woollins, Polyhedron, 2003, 22, 19. 

  17. 17. One ponytail will do: New partially fluorinated phosphine ligands with applications in fluorous biphasic solvent systems. M. L. Clarke, J. Organomet. Chem., 2003, 665, 65. 

  18. 18. Synthesis and transition metal chemistry of “phosphomide” ligands:  A comparision of the reactivity and electronic properties of diphenyl-P-perfluorooctanoylphosphine, P-acetyldiphenylphosphine and P-anisoyldiphenylphosphine,  R.A Baber, M. L. Clarke, A G. Orpen and D. A. Ratcliffe, J. Organomet. Chem., 2003, 667, 112.  

 

July 2003, Appointment as group leader in St Andrews.  All Papers below are with St Andrews affiliation.

 

  1. 19. Organometallic chemistry of bromodifluoromethyl substituted phosphines: the development of a novel nickel catalysed P-C bond forming reaction.  M. L. Clarke, A. G. Orpen, P. G. Pringle and E. Turley, J. Chem. Soc. Dalton Trans., 2003, 4393. 

  2. 20. Rhodium catalysed hydroformylation of unsaturated esters, M. L. Clarke, Tetrahedron Lett. 2004, 45, 4043. 

  3. 21. Organocatalysis gathers pace.  M. L. Clarke, Letters in Organic Chemistry, 2004, 1, 292.  

  4. 22. First microwave accelerated Hiyama couplings: clean cross-coupling of aryl chlorides within minutes. M. L. Clarke, Adv. Synth. Catal., 2005, 347, 303. 

  5. 23. Phenylphosphatrioxa-adamantanes: bulky, robust, electron-poor ligands which give very efficient rhodium(I) hydroformylation catalysts, M. L. Clarke, A. Marr, A. G. Orpen, P. G. Pringle, A. M. Ward, D. A. Zambrano-Williams, Dalton Trans., 2005, 1079. 

  6. 24. The electron-poor phosphines (C6F5)3P and (3,5-(CF3)2C6H3)3P do not mimic phosphites as ligands for hydroformylation. A comparision of the co-ordination chemistry of (C6F5)3P and (3,5-(CF3)2C6H3)3P and the low hydroformylation activity of their rhodium complexes.  M. L. Clarke, D. Elliss, K. L. Mason, A. G. Orpen, P. G. Pringle, R. Wingad and D. A. Zaheer, Dalton Trans., 2005, 1294. 

  7. 25. Branched selective hydroformylation:  A useful tool for organic synthesis., M. L. Clarke, Current Organic Chemistry, 2005, 9, 701 (Invited Review). 

  8. 26. The importance of steric effects on transmetalation, M. L. Clarke and M. Heydt, Organometallics, 2005, 24, 6475.   

  9. 27. Highly regioselective rhodium catalysed hydroformylation of unsaturated esters:  the first practical method for quaternary selective carbonylation.  M. L. Clarke and G. J. Roff, Chemistry: A Euro Journal, 2006, 12, 7978.  

  10. 28. Hydrogenation of aldehydes, ketones, imines, esters and anhydrides: reactivity and chemoselectivity.  M. L. Clarke and G. J. Roff, chap 11 in ‘The comprehensive handbook of homogeneous hydrogenation’; Ed’s J. H. N. deVries and C. J. Elsevier, 2006. 

  11. 29. Self- Assembly of organocatalysts:  a new approach to fine-tuning organocatalytic reactions.  M. L. Clarke and J. A. Fuentes, Angew. Chem. Int. Ed., 2007, 46, 930. 

  12. 30. Hydrogenation of aldehydes, ketones, imines, esters and anhydrides catalysed by a ruthenium complex of a chiral tridentate ligand, M. L. Clarke, M. B. Diaz-Venezuela, and A. M. Z. Slawin, Organometallics, 2007, 26, 16. 

  13. 31. A highly efficient process for regio-selective hydroformylation and hydroaminovinylation of methyl acrylate, M. L. Clarke and G. J. Roff, Green Chemistry, 2007, 9, 792. 

  14. 32. Diastereo- and enantio-selective hydrogenation of a fluorinated diketone, M. L. Clarke, M. B. France, J. J. R. Frew, F. G. Knight, G. J. Roff, Synlett, 2007, 11, 1739. 

  15. 33.  Microwave accelerated Suzuki coupling of aryl chlorides with electron deficient boronic acids.  J. A Fuentes, M. E. France, G. J. Roff, E. J. Milton, and M. L. Clarke, Beilstein Journal of Organic Chemistry, 2007, 3, art.18. 

  16. 34. The first organocatalytic carbonyl ene reaction: Isomerisation-free C-C bond formation promoted by H-bonding thio-ureas.  M. L. Clarke, C. E. S. Jones, M. B. France, Beilstein Journal of Organic Chemistry, 2007, 3, art. 24. 

  17. 35. Evaluation of C4 diphosphine ligands in rhodium catalysed methanol carbonylation under a syngas atmosphere: synthesis, structure, stability and reactivity of rhodium(I) carbonyl and rhodium (III) acetyl intermediates. G. W. Lamb, M. L. Clarke, A. M. Z. Slawin, B. Williams, and L. Key, Dalton Trans., 2007, 5582. 

  18. 36. A Supramolecular Approach to Modifying Chiral Ligands: Co-ordination Chemistry of a Multifunctionalised Tridentate Amine-Phosphine Ligand. J. A. Fuentes and M. L. Clarke, New J. Chem., 2008, 32, 689. 

  19. 37. Microwave accelerated Suzuki coupling of chloro-arylphosphine–oxides:  a method for introducing diversity into phosphine ligands.  K. Damian, M. L. Clarke and C. J. Cobley, J. Molecular Catalysis: Sect. A, 2008, 284, 46. 

  20. 38. A rationally designed catalyst for the Bayliss-Hillman reaction, C. E. S. Jones, S. M. Turega, M. L. Clarke, D. Philp, Tetrahedron Lett. 2008, 49, 4666. 

  21. 39. Hydroxy-carbonylation of alkenes catalysed by a palladium complex of a novel bulky P-chiral diphosphine ligand. J. J. R. Frew, M. L. Clarke, U. Meyer, R. P. Tooze. Dalton Trans. 2008, 1976.  

  22. 40. The carbonyl ene reaction: an atom-efficient C-C bond forming reaction for organic synthesis. M. L. Clarke and M. B. France, Tetrahedron, 2008, 64, 9003 (Commissioned Review). 

  23. 41. A mechanistic investigation into the elimination of phosphonium salts from a Rh / TRIPHOS methanol carbonylation catalyst, G. W. Lamb, M. L. Clarke, A. M. Z. Slawin, B. Williams, Dalton Trans., 2008, 4946. 

  24. 42. A new protocol for the deoxygenation of pyridine N-oxides by palladium catalysed transfer oxidation, J. A. Fuentes and M. L. Clarke, 2008, Synlett, 2579. 

  25. 43. Ligand electronic effects in homogeneous catalysis using transition metal complexes of phosphine ligands, M. L. Clarke and J. J. R. Frew, Specialist Periodical Reports: Organometallic Chemistry, Royal Society of Chemistry, Ed. I. J. S. Fairlamb and J. Lynam, 2009, vol. 35, 19. 

  26. 44. Iridium complexes of chiral diamines containing carbon and nitrogen stereocentres: synthesis, structure and evaluation as transfer hydrogenation catalysts, J. A. Fuentes, M. B. France, A. M. Z. Slawin and M. L. Clarke, New J. Chem. 2009, 33, 466, 

  27. 45. Enantioselective hydrogenation and transfer hydrogenation of bulky ketones catalysed by ruthenium complex of a chiral tridentate ligand, M. B. Diaz-Venezuela, S. D. Phillips, M. B. France, M. E. Gunn and M. L. Clarke, Chemistry, Euro. J., 2009, 15, 1227. 

  28. 46. Palladium-catalysed C-O bond formation using alkoxysilanes as nucleophiles, E. J. Milton, J. A. Fuentes and M. L. Clarke, Org. Bio. Chem. 2009, 7, 2645. 

  29. 47. Palladium catalysed P-C bond forming reactions of ortho-substituted aryl bromides, K. Damian, M. L. Clarke, C. J. Cobley, Appl. Organomet. Chem. 2009, 23, 272. 

  30. 48. Enantiomerically pure bis-(phosphanyl)carbaborane(12) compounds, S. Bauer, S. Tscirschwitz, P. Lonnecke, R. Frank, B. Kirchner, M. L. Clarke, and E. Hey-Hawkins,  Eur. J. Inorg. Chem., 2009, 2776. 

  31. 49. Reaction of a rhodium(I) carbonyl complex of a para-dimethylaminophenyl substituted diphosphine with methyl iodide and hydrogen iodide. G W. Lamb,­ D. Law, A. M. Z. Slawin and M. L. Clarke. Inorg. Chim. Acta. 2009, 362, 4263. 

  32. 50. Palladium complexes of new bulky bidentate phosphines are active and highly regioselective catalysts for the hydroxycarbonylation of styrene, J. J. R. Frew, K. Damian, H. Van Rensburg, A. M. Z. Slawin, R. P. Tooze, M. L. Clarke, Chem. Euro. J. 2009, 15, 10504. 

  33. 51. Palladium-catalysed Grignard cross-coupling using highly concentrated Grignards in methyl-tetrahydrofuran. E. J. Milton and M. L. Clarke, Green Chem. 2010, 12, 381. 

  34. 52. Regioselective and enantioselective hydroformylation of dialkyl acrylamides. G. M. Noonan, D. Newton, C. J. Cobley, A. Suárez, A. Pizzano, and M. L. Clarke, Adv. Synth. Catal. 2010, 352, 1047. 

  35. 53. On the NH effect in ruthenium catalysed hydrogenation of ketones; rational design of phosphine-amino-alcohol ligands for asymmetric hydrogenation of ketones, S. D. Phillips, J. A. Fuentes and M. L. Clarke, Chem. Euro. J. 2010, 16, 8002. 

  36. 54. Palladium complexes of bulky ortho-trifluoromethylphenyl-substituted phosphines; unusually regioselective catalysts for the hydroxycarbonylation and alkoxycarbonylation of alkenes A. Grabulosa, J. A. Fuentes, J. J. R. Frew, A. M. Z. Slawin and M. L. Clarke, J. Mol Catal. Sect. A. 2010, 330, 18. 

  37. 55. Asymmetric Hydroformylation of an Enantiomerically Pure Bicyclic Lactam; Efficient Synthesis of Functionalised Cyclopentylamines. G. M. Noonan, C. J. Cobley, T. Lebl and M. L. Clarke, Chem. Eur. J. 2010, 16, 12788. 

  38. 56. Highly Enantioselective Hydroxycarbonylation and Alkoxycarbonylation of Alkenes using Dipalladium Complexes as Pre-catalysts, T. M. Konrad, J. A. Fuentes, A. M. Z. Slawin and M. L. Clarke, Angew. Chem. Int. Ed. 2010, 49, 9197. 

  39. 57. Enantioselective reduction of benzofuranyl-aryl ketones, I. Carpenter and M. L. Clarke, Synlett, 2011, 65. 

  40. 58. On the rate-determining step and the ligand electronic effects in rhodium catalysed hydrogenation of enamines and the hydroaminomethylation of alkenes, J. A. Fuentes, G. J. Roff, P. Wawryzniak, M. Buhl, M. L. Clarke, Catal. Sci. Technol. 2011, 1, 431. 

  41. 59. Synthesis of organocatalysts using non-covalent chemistry; understanding the reactivity of ProNap, an enamine-type organocatalyst that can self assemble with complementary co-catalysts, J. A. Fuentes, T. Lebl, A. M. Z. Slawin, and M. L. Clarke, Chemical Science, 2011, 2, 1997. 

  42. 60. Exploring the role of phosphorus substituents on the enantioselectivity of Ru-catalysed ketone hydrogenation using tridentate phosphine-diamine ligands, S. D. Phillips, K. H. O. Andersson, N. Kann, M. T. Kuntz, M. B. France,  P. Wawrzyniak, and M. L. Clarke, Catal. Sci. Technol. 2011, 1, 1336. 

  43. 61. An asymmetric hydroformylation catalyst that delivers branched aldehydes from alkyl alkenes, G. M. Noonan, J. A. Fuentes, C. J. Cobley, and M. L. Clarke, Angew. Chem. Int. Ed. 2012, 51, 2477. 

  44. 62. Application of palladium (trioxo-adamantyl cage phosphine)chloride complexes as catalysts for the alkoxycarbonylation of styrene; Pd catalysed tert-butoxycarbonylation of styrene, J. A. Fuentes, A. M. Z. Slawin and M. L. Clarke, Catal. Sci. Technol. 2012, 2, 715. 

  45. 63. Convenient and improved protocols for the hydrogenation of esters at near-ambient temperatures using Ru catalysts derived from (P,P), (P,N,N) and (P,N,O) ligands. I. Carpenter, S. C. Eckelmann, M. T. Kuntz, J. A. Fuentes, M. B. France, M. L. Clarke, Dalton. Trans. 2012, 41, 10136. 

  46. 64. Recent developments in the homogeneous hydrogenation of esters, M. L. Clarke, Catal. Sci. Tech. 2012, 2, 2418. 

  47. 65. New phosphine-diamine and phosphine-amino-alcohol tridentate ligands for ruthenium catalysed enantioselective hydrogenation of ketones and a concise lactone synthesis enabled by asymmetric reduction of cyano-ketones. J. A. Fuentes, S. D. Phillips, and M. L. Clarke Chemistry Central Journal, 2012, 6, 151. 

  48. 66. The stability of imidazolidinones is the primary influence on the catalytic activity of proline-amides and proline sulfonamides in enamine catalysis using alkyl aldehyde substrates, S. Tin, J. A. Fuentes, T. Lebl and M. L. Clarke, Eur. J. Org. Chem., 2013, 141. 

  49. 67. Remarkable Lewis acid catalytic performance of the scandium trimesate metal organic framework MIL-100(Sc) for C–C and C-N bond-forming reactions, L. Mitchell, B. Gonzalez-Santiago, J. P. S. Mowat, M. E. Gunn, P. Williamson, N. Acerbi, M. L. Clarke and P. A. Wright, Catal. Sci. Tech., 2013, 2013, 3, 606. 

  50. 68. Asymmetric Hydroformylation, Hydroxy- and Alkoxycarbonylation for Stereoselective Synthesis, J. T. Durrani & M. L. Clarke, in Stereoselective Synthesis of Drugs and Natural Products, Wiley, 2013. 

  51. 69. Carbonylation of alkenes, J. A. Fuentes and M. L. Clarke, Chapter 1.1.6 in Science of Synthesis C-1 Building Blocks in Organic Synthesis 1: Additions to Alkenes, Alkynes, and Carbonyl Compounds. Ed. P. W. N. M. van Leeuwen, Georg Thieme, Stuttgart, Germany 2013. 

  52. 70.  Carbonylation of alkynes, J. A. Fuentes and M. L. Clarke, Chapter 1.2.1 in Science of Synthesis C-1 Building Blocks in Organic Synthesis 1: Additions to Alkenes, Alkynes, and Carbonyl Compounds. Ed. P. W. N. M. van Leeuwen, Georg Thieme, Stuttgart, Germany 2013. 

  53. 71. Simultaneous control of regioselectivity and enantioselectivity in the hydroxycarbonylation and methoxycarbonylation of vinyl arenes, T. M. Konrad, J. T. Durrani, C. J. Cobley, and M. L. Clarke, Chem. Commun. 2013, 49, 3306. 

  54. 72. Highly enantioselective hydrogenation of cycloalkyl and heterocyclic ketones catalysed by an iridium complex of a tridentate phosphine-diamine ligand J. A. Fuentes, I. Carpenter, N. Kann, and M. L. Clarke, Chem. Commun. 2013, 49, 10245. 

  55. 73. Rhodium / Phospholane-phosphite catalysts give unusually high regioselectivity in the enantioselective hydroformylation of vinyl arenes, G. M. Noonan, C. J. Cobley, T. Mahoney, M. L. Clarke, Chem. Commun. 2014, 50, 1475. 

  56. 74. Catalytic hydrogenation of low-reactivity carbonyl groups using bifunctional chiral tridentate ligands. M. L. Clarke, Synlett, 2014, 25, 1371. 

  57. 75. Catalytic constructive deoxygenation of lignin-derived phenols: new C-C bond formation processes from imidazole-sulfonates and ether cleavage reactions, S. M. Leckie, G. L. Harkness and M.L. Clarke, Chem. Commun. 2014, 50, 11511. 

  58. 77. Hydrogenation of unactivated enamines to tertiary amines: rhodium complexes of fluorinated phosphines give marked improvements in catalytic activity, S. Tin, T. Fanjul, M. L. Clarke, Bielstein J. Org. Chem. 2015, 11, 622. 

  59. 78. On the functional group tolerance of ester hydrogenation and polyester depolymerisation catalysed by ruthenium complexes of tridentate amino-phosphine ligands, J. A. Fuentes, S. M. Smith, M. T. Scharbert, I. Carpenter, D. B. Cordes, A. M. Z. Slawin, and M. L Clarke, Chem. Eur. J. 2015, 21, 10851. 

  60. 79. Rapid asymmetric transfer hydroformylation of disubstituted alkenes using paraformaldehyde as a syngas surrogate, J. A. Fuentes, R. Pittaway and M. L. Clarke, Chem. Eur. J. 2015, 21, 10645. 

  61. 80. A modular family of phosphine-phosphoramidite ligands and their hydroformylation catalysts: Steric tuning impacts upon the coordination geometry of trigonal bipyramidal complexes of type [Rh(H)(CO)2(P^P*)], R. C. How, R. Hembre, J. A. Ponasik, G. S. Tolleson, and M. L. Clarke, published on the web: DOI: 10.1039/C5CY00886G.