Burns Lab Palladium(II/IV) Hayden Anderson • Competing β-Hydride Elimination • Higher Stability • Higher Selectivity • Limited β-Hydride Elimination • Unstable Intermediate • Lower Selectivity Reviews: • Chem. Rev. 2010, 110, 824 • Chem. Sci., 2015, 6, 70 Major Players: • Chem. Rev. 2010, 110, 1147 Dr. Allan J. Canty • Standard Pd0/PdII Cycle 1972 Monash University (Ph.D.) • Used by most cross-coupling reactions University of Tasmania (Professor Emeritus) Dr. Melanie Sanford 1996 Yale University (B. Sc. & M. Sc.) 2001 California Institute of Technology (Ph.D.) 2003 Princeton University (Post-doc) 2007 University of Michigan (Assistant Professor) 2010 University of Michigan (Associate Professor) 2016-Present University of Michigan (Professor) Dr. David Milstein 1968 The Hebrew University of Jerusalem (B. Sc.) 1969 The Hebrew University of Jerusalem (M. Sc.) 1976 The Hebrew University of Jerusalem (Ph.D.) • Used by Heck-type couplings 1977 Colorado State University (Post-doc) 1979 DuPont Co. 1987 Weizmann Institute of Science (Associate Professor) 1993-present Weizmann Institute of Science (Professor) Burns Lab Palladium(II/IV) Hayden Anderson J. Am. Chem. Soc. 2004, 126, 9542 J. Am. Chem. Soc. 2004, 126, 2300 Org. Lett. 2006, 8, 1141 Acc. Chem. Res. 2012, 45, 936 J. Am. Chem. Soc. 2010, 132, 12203 J. Am. Chem. Soc. 2010, 132, 12203 J. Am. Chem. Soc. 2010, 132, 12203 Burns Lab Palladium(II/IV) Hayden Anderson Via: J. Am. Chem. Soc. 2005, 127, 14560 J. Am. Chem. Soc. 2017, 139, 643 J. Am. Chem. Soc. 2008, 130, 16184 J. Am. Chem. Soc. 2012, 134, 7 J. Am. Chem. Soc. 2009, 131, 10806 J. Am. Chem. Soc. 2006, 128, 7134 J. Am. Chem. Soc. 2006, 8, 2523 J. Am. Chem. Soc. 2014, 136, 4097 Angew. Chem., Int. Ed. Engl. 2012, 51, 2225 J. Am. Chem. Soc. 2008, 130, 13552 J. Am. Chem. Soc. 2011, 133, 7577 Burns Lab Palladium(II/IV) Hayden Anderson Angew. Chem., Int. Ed. Engl. 1997, 36, 119 J. Organomet. Chem. 2004, 689, 3741 Marta Catellani • Ph.D. from University of Parma • Postdoc at University of Chicago • Moscow State University (1992) • Beijing Institute of Technology (2004) • University of Xi’an (2004) Org. Lett. 2006, 8, 4827 • University of Parma (Present) Tetrahedron Lett. 2004, 45, 6903 Tetrahedron 2008, 64, 6002 Angew. Chem., Int. Ed. 2007, 46, 1485 Angew. Chem., Int. Ed. 2009, 48, 1447 Burns Lab Palladium(II/IV) Hayden Anderson Angew. Chem. Int. Ed. 2013, 52, 5305 J. Am. Chem. Soc. 2013, 135, 9318 Angew. Chem. Int. Ed. 2021, 60, 5141 Angew.Chem. Int. Ed. 2019, 58,2144 Burns Lab Palladium(II/IV) Hayden Anderson Tetrahedron Lett. 1975, 2225 J. Am. Chem. Soc. 2006, 128, 7179 Angew. Chem., Int. Ed. 2007, 46, 5737 J. Org. Chem. 2010, 75, 6294 Org. Lett. 2008, 10, 793 Org. Lett. 2009, 11, 1147 J. Am. Chem. Soc. 2005, 127, 14586 Tetrahedron 2007, 63, 7009 J. Am. Chem. Soc. 2018, 140, 1207 J. Am. Chem. Soc. 2009, 131, 45, 16354 J. Am. Chem. Soc. 2008, 130, 2962 Angew.Chem. Int. Ed. 2019, 58,2144 Tetrahedron 2007, 63, 7009 Org. Lett. 2016, 18, 5, 960 Burns Lab Palladium(II/IV) Hayden Anderson Chem. Rev., 2010, 110, 824 J. Am. Chem. Soc. 1985, 107, 1781 J. Org. Chem. 1997, 62, 7295 J. Am. Chem. Soc. 2007, 129, 4906 Tetrahedron Lett., 1987, 28, 1611 Tetrahedron 2008, 64, 9874 a Chem. Eur. J. 2008, 14, 6697 [PdII] a:b Pd(OAc)2 1:16.9 Pd(OAc)2(PPh3)2 1:2.9 b Pd(OAc)2[P(o-Tol)3]2 1:2.4 Tetrahedron Lett. 1985, 26, 4887 J. Am. Chem. Soc. 2007, 129, 5836.