Chapter 20: More about Oxidation-Reduction ReactionsLearning Objectives:1. Be able to predict products from reductions.2. Be able to predict products from oxidation of alcohol, aldehydes, ketones, and alkenes.3. Be able to predict products from hydroxylation of alkenes along with the associated stereochemistry.4. Be able to predict products from oxidative cleavage of 1,2-diols, alkenes, and alkynes.5. Be able to write the general electron-pushing (arrow-pushing) mechanisms of ozonlysis and Baeyer-Villiger reaction.6. Be able to employ the reactions taught in Chem2310 and Chem2320 for multiple step synthesis and functional group interconversion.Sections:20.1 Reduction Reactions*20.2 Oxidation of Alcohols*20.3 Oxidation of Aldehydes and Ketones*20.4 Oxidation of Alkenes with Peroxyacids20.5 Designig a Synthesis VII: Controlling Stereochemistry#20.6 Hydroxylation of Alkenes20.7 Oxidative Cleavage of 1,2-Diols20.8 Oxidative Cleavage of Alkenes20.9 Oxidative Cleavage of Alkynes#20.10 Designing a Synthesis VII: Functional Group Interconversion20.11 Biological Oxidation-Reduction Reaction#20.12 Oxidation of Hydroquinones and Reduction of Quinones#* Sections that will be focused# Sections that will be skippedRecommended additional problems20.34 – 20.42, 20.44 – 20.53, 20.60 – 20.651Class Note20.1 Reduction ReactionsA.H2Pd, Pt, or NiH2Pd, Pt, or NiB.H2, Pd/CquinolineLindlarcatalystC.OH2Raney NiHOH2Raney NiD.LindlarcatalystClOE.HNH2Pd/C2F.Na or LiNH3 (liq.)G. OHO1) NaBH42) H3O+1) NaBH42) H3O+OCH2CH3ONHCH2CH3O1) NaBH42) H3O+1) NaBH42) H3O+H.1) LiAlH42) H3O+OHOOCH2CH3ONHCH2CH3O1) LiAlH42) H3O+1) LiAlH42) H3O+1) LiAlH42) H3O+3I.H2Raney Ni1) NaBH42) H3O+1) LiAlH42) H3O+OOOCH3?OOH20.2 Oxidation of Alcohols and 20.3Oxidation of Aldehydes and KetonesA. OHOHCrO3H2SO4Na2Cr2O7H2SO4H2CrO4OH4B.OOCrO3H2SO4Na2Cr2O7H2SO4C.OHPCCD. Swern oxidationOH(COCl)2CH3SOCH3(DMSO)5E. Baeyer-Villiger oxidation(i)CH2CH3RCO3HOCH2CH3RCO3HO(ii) Mechanism(iii) Relative migration tendencyH > 3° alkyl > 2° alkyl > 1° alkyl > methyl620.4 Oxidation of Alkenes with PeroxyacidsA. RRCO3H+B. Mechanism720.6 Hydroxylation of Alkenes and 20.7 Oxidative Cleavage of 1,2-DiolsA.1) OsO4, H2O22) H2OB. CH3OHOHHIO4820.8 Oxidative Cleavage of AlkenesA. Ozonolysis1) O3, -78oC2) work-upB. Mechanism of the first stepC. Examples(i)1) O3, -78oC2) Zn1) O3, -78oC2) H2O29(ii)1) O3, -78oC2) Zn1) O3, -78oC2) (CH3)2S(iii)1) O3, -78oC2) (CH3)2S1) O3, -78oC2) H2O21020.10 Designing a Synthesis VII: Functional Group
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