M.C. White, Chem 153 Nu attack on olefins -329- Week of November 25, 2002 Oxidation of terminal olefins Standard Wacker conditions Selective oxidation of terminal olefins PdCh(cat) CuCh(cat. yo DMF/HO Chadha Chem Soc. perkin /1979 2346 Cuprous chloride(Cucyozas the oxidant system leads to faster reactions with no chlorinated biproducts H H PdCl(30 mol%) PC2(20mo%) CuCI(1.6 CuCI(10 mol%)O, DMF/H2O(10: 1.2) DMF/H0(9: 1) H OTHI 77 H OTHP OTBS 91% Ikegami Tetrahedron 1981(37)4411 Cu(oAc)O, oxidant system Benzoquinone can be used as a stoichiometric oxidant. H Pd(oAch(10 mol%) PdCh(10 mol%) HCIO4(0.3M), CH3CN ao cose 20 mayo H H Smith JACS1999(121)10468 Santelli tl1994(35)6481M.C. White, Chem 153 Nu attack on Olefins -329- Week of November 25, 2002 Oxidation of terminal olefins Selective oxidation of terminal olefins O PdCl2 (cat.) CuCl2 (cat.)/O2 DMF/H2O O O 70% Chadha J. Chem. Soc. Perkin I 1979 2346. Cuprous chloride (CuCl)/O2 as the oxidant system leads to faster reactions with no chlorinated biproducts. H H OTHP O H H OTHP O O PdCl2 (30 mol%) CuCl (1.6 eq)/O2 DMF/H2O (10:1.2) 77% Ikegami Tetrahedron 1981 (37) 4411. H PdCl2 (20 mol%) CuCl (10 mol%)/O2 DMF/H2O (9:1) 91% OTBS O O H OTBS O O O Money Tetrahedron 1996 (52) 6307. Benzoquinone can be used as a stoichiometric oxidant: H H H O O H Pd(OAc)2 (10 mol%) HClO4 (0.3M), CH3CN O O 85% H H H O O H O Santelli TL 1994 (35) 6481. Cu(OAc)2/O2 oxidant system: O O PdCl2 (10 mol%) Cu(OAc)2 (20 mol%)/O2 DMF: H2O (7:1) O O O Smith JACS 1999 (121) 10468. Standard Wacker conditions: