columbia大学有机化学课件 （三十五）.pptVIP

8.14Sulfonate EstersasSubstrates in Nucleophilic Substitution Leaving Groups we have seen numerous examples of nucleophilic substitution in which X in RX is a halogen halogen is not the only possible leaving group though Other RX compounds undergo same kinds of reactions as alkyl halides Preparation (abbreviated as ROTs) Tosylates undergo typical nucleophilic substitution reactions The best leaving groups are weakly basic Table 8.8Approximate Relative Reactivity of Leaving Groups Leaving Group Relative Conjugate acid Ka of Rate of leaving group conj. acid F– 10-5 HF 3.5 x 10-4 Cl– 1 HCl 107 Br– 10 HBr 109 I– 102 HI 1010 H2O 101 H3O+ 56 TsO– 105 TsOH 600 CF3SO2O– 108 CF3SO2OH 106 Table 8.8Approximate Relative Reactivity of Leaving Groups Leaving Group Relative Conjugate acid Ka of Rate of leaving group conj. acid F– 10-5 HF 3.5 x 10-4 Cl– 1 HCl 107 Br– 10 HBr 109 I– 102 HI 1010 H2O 101 H3O+ 56 TsO– 105 TsOH 600 CF3SO2O– 108 CF3SO2OH 106 Tosylates can be converted to alkyl halides Tosylate is a better leaving group than bromide. Tosylates allow control of stereochemistry Preparation of tosylate does not affect any of the bonds to the stereogenic center, so configuration and optical purity of tosylate is the same as the alcohol from which it was formed. Tosylates allow control of stereochemistry Having a tosylate of known optical purity and absolute configuration then allows the preparation of other compounds of known configuration by SN2 processes. 8.15Looking Back: Reactions of AlcoholswithHydrogen Halides Secondary alcohols react with hydrogen halides with net inversion of configuration Secondary alcohols react with hydrogen halides with net inversion of configuration Most reasonable mechanism is SN1 with front side of carbocation shielded by leaving group Rearrangements can occur in the reaction of alcohols with hydrogen halides Rearrangements can occur in the reaction o