M.C. White. Chem 153 Nu attack on olefins-334- Week of november 25. 2002 Tandem sequences Oxo-palladation/intermolecular Heck CO,Me CO,Me Pd(OAch(10 mol%) d CuCl(1 eq)o, DMF (or Ph) B-hydride elimination is not option for this intermediate Pd(C)2(10mo9%) CuCh(3 eq), Meoh 30% of the IOMe furan product te: O, is not necessary to re-oxidize pd if supra-stoichiometric amounts of Cu(ln) salts Semmelhack JACS 1984(106)1496 are used OMe o OMe OMe m Pd(ci)(10 mol%) CuCl2 (3 eq), MeOH CO CO,Me COMe 70%(mans:cs,3:1) Semmelhack JACS 1982(104)5850M.C. White, Chem 153 Nu attack on Olefins -334- Week of November 25, 2002 OH Pd(OAc)2 (10 mol%) CuCl (1 eq)/O2, DMF CO2Me O PdII AcO CO2Me (or Ph) O CO2Me 89% Semmelhack TL 1993 (34) 7205. β-hydride elimination is not an option for this intermediate Oxo-palladation/intermolecular Heck R OH Pd(Cl)2 (10 mol%) CuCl2 (3 eq), MeOH CO R O PdII CO L Cl R O O Pd(Cl)Ln HOMe R O O OMe note: O2 is not necessary to re-oxidize Pd if supra-stoichiometric amounts of Cu(II) salts are used 70% + 30% of the furan product Semmelhack JACS 1984 (106) 1496. Oxo-palladation/carbonylation OMe O O Pr OH CO OMe O O O Pr PdII L Cl CO OMe O O O Pr CO2Me Pd(Cl)2 (10 mol%) CuCl2 (3 eq), MeOH OH O O O Pr CO2Me 70% (trans:cis ,3:1) Semmelhack JACS 1982 (104) 5850. Tandem sequences