M.C. White, Chem 153 JT-Allyl chemistry -346 Week of December 2. 2002 Mechanism Substitution with immersion CO,Me Pd(dba) THF. 50C CO,B leOC LaPd(cn CO2Bn Meo2C lmPd CO,Bn Stille!S198410483 BuaSnCI Amine nucleophiles: CO,M Pd(PPh3)43-8 mol% COmE CO,Me THF rt 2N NHR NHR 81%(2: 3 identity of major isomer is not specified) MeO,C Meog -OAc) MeO2c F +(-OAc NpD(OAc) L.Pall Trost JOC 1979(44)3451M.C. White, Chem 153 π-Allyl chemistry -346- Week of December 2, 2002 CO2Me Cl Pd(dba)2 n-Bu3Sn CO2Bn THF, 50oC CO2Me CO2Bn Pd0Ln LnPdII MeO (Cl) 2C n-Bu3Sn CO2Bn n-Bu3SnCl LnPdII MeO2C CO2Bn RE 87% OA via SN2 Mechanism Substitution with inversion: Stille JACS 1984 (106) 4833. CO2Me OAc H2N OMe OMe Pd(PPh3)4 3-8 mol% THF, rt CO2Me NHR CO2Me NHR + 81% (2:3 identity of major isomer is not specified) (OAc) MeO2C LnPdII Pd0Ln MeO2C (-OAc) LnPdII + NH2R MeO2C (-OAc) LnPdII (+NH2R) Amine nucleophiles: Trost JOC 1979 (44) 3451