M.C. White, Chem 153 Nu attack on olefins -331 Week of novem ber 25. 2002 Cyclic ether formation Pd(oAch(20 mol%) Cu(OAch(50 mol%)o Meoh/ho Pd(oac)2 Pd(oac)z 2Cu(OA)、/12O2 OAc Cycle A Cvcle B +2 HOAc <甲 2 Cu(oAch H20 HOAc H10::1mm!m195(48)153. Asymmetric version 5 membered ring formation Pd(ococF3h2(10 (S, S-boxax(10 D mol%) Meoh OH 0 5-exo-trig 6 membered ring formation Pd(ococF3)2 (10 mol%) (S, S)boxx(10 mol%) oOCOCF3 OCOCF3 6-exo-trig 61% yield Hayashi JACS 1997(119)506 97%eeM.C. White, Chem 153 Nu attack on Olefins -331- Week of November 25, 2002 N O R O N R PdII OCOCF3 OCOCF3 Asymmetric version: OH Pd(OCOCF3)2 (10 mol%) (S,S)-boxax (10 mol%) MeOH O O (4 eq) O OH Pd(OCOCF3)2 (10 mol%) (S,S)-boxax (10 mol%) MeOH O O (4 eq) 5 membered ring formation 6 membered ring formation O * 71 % yield 93 % ee 61 % yield Hayashi 97 % ee JACS 1997 (119) 5063. OH Pd(OAc)2 (20 mol%) Cu(OAc)2 (50 mol%)/O2 MeOH/H2O O 54% OH PdII O OAc O O PdII H O O HOAc LnPdII H OAc Pd(OAc)2 LnPd0 Pd(OAc)2 HOAc 2 Cu(OAc)2 2 Cu(OAc) 1/2 O2 + 2 HOAc H2O Cycle A Cycle B Hosokawa Bull. Chem. Soc. Jpn. 1975 (48) 1533. Cyclic ether formation 5-exo-trig 5-exo-trig 6-exo-trig