Page 12 - From -Arylation of Olefins to Acylation with Aldehydes: A Journey in Regiocontrol of the Heck Reaction
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R-Arylation of Olefins to Acylation with Aldehydes Ruan and Xiao


          Jianliang Xiao received his B.Eng. in chemical engineering at  10 Deeth, R. J.; Smith, A.; Brown, J. M. Electronic control of the regiochemistry in palladium-
          Northwest University. This was followed by a M.Eng. in catalytic  phosphinecatalyzedintermolecularHeckreactions.J.Am.Chem.Soc.2004,126,7144–7151.
          engineering with Profs. Chi Wu and Junyu Wang at the Research  11 Henriksen, S. T.; Norrby, P.-O.; Kaukoranta, P.; Andersson, P. G. Combined experimental
                                                                  and theoretical study of the mechanism and enantioselectivity of palladium-catalyzed
          Institute of Petroleum Processing and a Ph.D. in chemistry with Prof.  intermolecular Heck coupling. J. Am. Chem. Soc. 2008, 130, 10414–10421.
          Marty Cowie at the University of Alberta. After a postdoctoral  12 (a) Bengston, A.; Larhed, M.; Hallberg, A. Protected indanones by a Heck-aldol annulation
          appointment with Prof. Richard Puddephatt, he joined the ERATO  reaction. J. Org. Chem. 2002, 67, 5854–5856. (b) Olofsson, K.; Larhed, M.; Hallberg, A.
                                                                  Highly regioselective palladium-catalyzed internal arylation of allyltrimethylsilane with aryl
          Molecular Catalysis Project directed by Prof. Noyori. In 1996 he  triflates. J. Org. Chem. 1998, 63,5076–5079. (c) Larhed, M.; Hallberg, A. Direct synthesis
          took up a Principal Scientist position at the University of Liverpool  of cyclic ketals of acetophenones by palladium-catalyzed arylation of hydroxyalkyl vinyl
                                                                  ethers. J. Org. Chem. 1997, 62,7858–7862. (d) Karabelas, K.; Westerlund, C.; Hallberg,
          and was appointed to a Lectureship in the Chemistry Department  A. The effect of added silver nitrate on the palladium-catalyzed arylation of allyltrimethyl-
          in 1999; this was followed by promotion to full Professor in early  silanes. J. Org. Chem. 1985, 50, 3896–3900.
          2005. He was awarded the UK Prize for Process Chemistry  13 (a) Cabri, W.; Candiani, I.; Bedeschi, A.; Santi, R. 1,l0-Phenanthroline derivatives: a new
                                                                  ligand class in the Heck reaction. Mechanistic aspects. J. Org. Chem. 1993, 58, 7421–
          Research 2008.
                                                                  7426. (b) Cabri, W.; Candiani, I.; Bedeschi, A.; Santi, R. Palladium-catalyzed arylation of
                                                                  unsymmetrical olefins. Bidentatephosphine ligand controlled regioselectivity. J. Org. Chem.
          We are indebted to all our co-workers and collaborators and in  1992,57,3558–3563. (c) Cabri,W.;Candiani,I.;Bedeschi, A.;Santi, R. Ligand-controlled
                                                                  R-regioselectivity in palladium-catalyzed arylation of butyl vinyl ether. J. Org. Chem. 1990,
          particular to those involved in this study for their invaluable  55,3654–3655.
                                                               14 Xu, L.; Chen, W.; Ross, J.; Xiao, J. Palladium-catalyzed regioselective arylation of an
          intellectual and experimental contributions. Their names are seen
                                                                  electron-rich olefin by aryl halides in ionic liquids. Org. Lett. 2001, 3, 295–297.
          in the references cited. We also acknowledge the EPSRC (EP/  15 Mo, J.; Xu,L.; Xiao, J.Ionicliquid-promoted, highlyregioselectiveHeckarylationof electron-
                                                                  rich olefins by aryl halides. J. Am. Chem. Soc. 2005, 127,751–760.
          F000316 and EP/C005643), Pfizer, AstraZeneca, NPIL Pharma
                                                               16 Pei, W.; Mo, J.; Xiao, J. Highly regioselective Heck reactions of heteroaryl halides with
          UK, Johnson Matthey, and the University of Liverpool for  electron-rich olefins in ionic liquid. J. Organomet. Chem. 2005, 690, 3546–3551.
          financial support.                                   17 Hyder, Z.;Mo,J.;Xiao, J.Palladium-catalyseddirect regioselectivesynthesisof cyclic ketals
                                                                  from electron-rich olefins and aryl bromides in ionic liquids. Adv. Synth. Catal. 2006, 348,
                                                                  1699–1704.
          FOOTNOTES                                            18 Mo, J.; Liu, S.; Xiao, J. Palladium-catalyzed regioselective Heck arylation of electron-rich
                                                                  olefins in a molecular solvent-ionic liquid cocktail. Tetrahedron 2005, 61, 9902–9907.
          *To whom correspondence should be addressed. Telephone: (44)-151-7942937. Fax:
          (44)-151-7943588. E-mail: j.xiao@liv.ac.uk.          19 Mo, J.; Xu, L.; Ruan, J.; Liu, S.; Xiao, J. Regioselective Heck arylation of unsaturated
                                                                  alcohols by palladium catalysis in ionic liquid. Chem. Commun. 2006, 3591–3593.
                                                               20 Chalk, A. J.; Magennis, S. A. Palladium-catalyzed vinyl substitution reactions. I. New
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