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Unformatted text preview: MoOPH RO N O R'' R' N C O R RCO 2 R' R SR' O R N O OH R' R R' R''O R R' R''O OH R R' R''O OR''' RO X O N C N R' R N NR'' 2 R R' O O R CH 3 O R N O R''' R'' RCX 2 R' S S R R' RCX 3 N N O R' R R'' R''' RO SR' S R R' N OR'' R R' N R'' C N R R R' R''O NR 2 ''' O R R' Myers Oxidation States of Organic Functional Groups Alcohol General Introductory References March, J. In Advanced Organic Chemistry , John Wiley and Sons: New York, 1992 , p. 1158-1238. Carey, F. A.; Sundberg, R. J. In Advanced Organic Chemistry Part B , Plenum Press: New York, 1990 , p. 615-664. Carruthers, W. In Some Modern Methods of Organic Synthesis 3rd Ed. , Cambridge University Press: Cambridge, UK, 1987 , p. 344-410. Mark G. Charest Chem 115 Oxidation The notion of oxidation state is useful in categorizing many organic transformations. This is illustrated by the progression of a methyl group to a carboxylic acid in a series of 2- electron oxidations, as shown at right. Included are several functional group equivalents considered to be at the same oxidation state. Alkane R-CH 3 Alcohol R-CH 2 OH (R-CH 2 X ) Aldehyde (Ketone) R-CHO (RCOR') Carboxylic Acid R-CO 2 H Carbonic Acid Ester ROH + CO 2 (ROCO 2 H) organometallics in general RCH 2 M (M = Li, MgX, ZnX...) alkyl halide X = halide alkyl ether X = OR' alkylthio ether X = SR' alkylamine X = NR' 2 alkyl azide X = N 3 alkane sulfonate X = OSO 2 R' hemiketal (hemiacetal) ketal (acetal) dithiane oxime hydrazone geminal dihalide enol ether (enamine) ester orthoester nitrile ketene trihalomethyl hydroxamic acid alkyl haloformate carbamate xanthate isocyanate carbodiimide aminal thioester amide urea Summary of Reagents for Oxidative Functional Group Interconversions: Fetizon's Reagent Dimethylsulfoxide-Mediated Oxidations Dess-Martin Periodinane (DMP) o-Iodoxybenzoic Acid (IBX) tetra- n-Propylammonium Perruthenate (TPAP) N-Oxoammonium-Mediated Oxidation Manganese Dioxide Barium Manganate Oppenauer Oxidation Chromium (VI) Oxidants Sodium Hypochlorite N-Bromosuccinimide (NBS) Bromine Cerium (IV) Oxidants imine organoboranes RCH 2 BR 2 ' organosilanes RCH 2 SiR 3 ' Aldehyde Sodium Chlorite Potassium Permanganate Aldehyde Ketone Baeyer-Villiger Oxidation Alcohol Ruthenium Tetroxide Ketone Davis Oxaziridine Diol O 2 /Pt N-Oxoammonium-Mediated Oxidation O 2 /Pt Jones Oxidation Silver Oxide Pyridinium Dichromate (PDC) Lactone -Hydroxy Ketone Acid Ester Ester Acid Aldehyde or Ketone Corey-Gilman-Ganem Oxidation Rubottom Oxidation Bromine (OBO ester shown) R C H 2 O H ( C H 3 ) 2 S O H R O S C H 2 C H 3 H X ( C H 3 ) 2 S E H + R O H X ( C H 3 ) 2 S H H R O S C H 3 C H 3 X O O H C H 3 H O H 3 C O H H 3 C S P h O H O O H C H 3 H O H 3 C O H H 3 C S P h O A c H O O B n H O H O ( C H 3 ) 2 S R O H H 2 C S C H 3 H + R O S C H 3 H O O C H 3 O T B S B H + R C O 2 O O C H 3 O T B S H O T B S O T B S O H O O O H C H 3 H O H 3 C O H H 3 C S P h H O O H C H 3 H O H 3 C O H H 3 C S P h O H H H R O A c O B A l c o h o...
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This test prep was uploaded on 04/06/2008 for the course CHEM 215 taught by Professor Shair during the Fall '07 term at Harvard.
- Fall '07
- Organic chemistry