Chapter 19: 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:19.1 Reduction Reactions*19.2 Oxidation of Alcohols*19.3 Oxidation of Aldehydes and Ketones*19.4 Designig a Synthesis VIII: Controlling Stereochemistry#19.5 Hydroxylation of Alkenes19.6 Oxidative Cleavage of 1,2-Diols19.7 Oxidative Cleavage of Alkenes19.8 Oxidative Cleavage of Alkynes#19.9 Designing a Synthesis IX: Functional Group Interconversion* Sections that will be focused# Sections that will be skippedRecommended additional problems19.30 – 19.37, 19.39 – 19.49, 19.56 – 19.611Class Note19.1 Reduction Reactions*A.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?OOH19.2 Oxidation of Alcohols* and 19.3 Oxidation of Aldehydes and Ketones*A. 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 > methyl619.4 Designig a Synthesis VIII: Controlling StereochemistryA. Oxidation of Alkenes with PeroxyacidsRRCO3H+B. Example719.5 Hydroxylation of Alkenes and 19.6 Oxidative Cleavage of 1,2-DiolsA.1) OsO4, H2O22) H2OB. CH3OHOHHIO4819.7 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) H2O21019.9 Designing a Synthesis IX: Functional Group
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