第四章 Oxidation and Reduction.ppt

第四章 Oxidation and Reduction 4.7 Allylic oxidation of alkenes Selenium Dioxide (SeO2) Ene-type reaction(A), sigmatropic [2,3]-shift (B), selenium ester (C), allylic alcohol (D) Chromic anhydride (CrO3) Powerful oxidant suitable for electron-deficient alkenes PCC or pyridine-CrO3: Electron-rich ?-systems t-Butyl perbenzoate 4.8 Terminology for reduction of carbonyl compounds 4.9 Nucleophilic reducing agents Aluminum Hydrides Lithium Aluminum hydride (LiAlH4) Hydride consumption in LiAlH4 reductions The reactivity of LiAlH4 may be tempered by dialkyl amines Partially replacing the hydrides, the resultant reagent is less reactive. Rosenmund procedure Na[AlH2(OCH2CH2OCH3)] sodium bis(2-methoxyethoxy)aluminum hydride, Red-Al A versatile, commercially available reducing agent Borohydrides Sodium borohydride (NaBH4) Soluble in diglyme and hydroxylic solvents Lithium borohydride (LiBH4) Lithium cation is stronger Lewis acid than sodium cation, so that lithium borohydride is more powerful reducing reagent. Zinc borohydride (Zn(BH4)2) ● Less basic and suitable for base-sensitive compounds ● Better coordinating ability ● Besides aldehydes and ketones, reduces aliphatic esters and carboxylic acid. ● Hydroborating agent for alkenes, dienes, and alkynes. * 4.1 Oxidation of alcohols to aldehydes and ketones Classical procedure: Chromium (VI) reagent Some reagents can obviate the toxicity of Chromium (VI). Methods for oxidation of alcohol: Oxidation mechanism: E2-like process. Deuterium substitution of the ?-H in isopropanol slows the rate of chromic acid oxidation by sevenfold. ?-H is removed in a slow step Relative rate 4.2 reagent and procedures for alcohol oxidation Jones reagent Excellent reagent for alcohols that do not contain acid-sensitive groups. Excess Cr (VI) is destroyed by adding some isopropanol. Collins-Ratcliff reagent 2C5H5N: a mild reagent for alcohols that contain acid-sensitive groups. But, to achieve rapid and complete oxidation, a large