p 251 Alkenes Alkynes I Prepapration of alkenes

p. 251

Alkenes & Alkynes I. Prepapration of alkenes 1. Dehydrohalogenation 2. Dehydration

Alkenes & Alkynes II. Reactions of alkenes & alkynes A. Electrophilic Additions to Alkenes 1. Hydrohalogenation 2. Halogenation 3. Halohydrins 4. Hydration

Alkenes & Alkynes II. Reactions of alkenes & alkynes A. Electrophilic Additions to Alkenes 1. Hydrohalogenation (Chapter 7)

Alkenes & Alkynes II. Reactions of alkenes & alkynes A. Electrophilic Additions to Alkenes 2. Halogenation

Electrophilic addition of Br 2 to an alkene

p. 217

p. 218

Alkenes & Alkynes II. Reactions of alkenes & alkynes A. Electrophilic Additions to Alkenes 2. Halogenation (working backwards)

Alkenes & Alkynes II. Reactions of alkenes & alkynes A. Electrophilic Additions to Alkenes 3. Halohydrins

Alkenes & Alkynes II. Reactions of alkenes & alkynes A. Electrophilic Additions to Alkenes 4. Hydration i. acid catalyzed

Alkenes & Alkynes II. Reactions of alkenes & alkynes A. Electrophilic Additions to Alkenes 4. Hydration ii. oxymercurication

Alkenes & Alkynes II. Reactions of alkenes & alkynes A. Electrophilic Additions to Alkenes 4. Hydration iii. Hydroboration & oxidation

p. 223

d d + - d + d - Fig. 7 -4, p. 225

Jmol

Alkenes & Alkynes II. Reactions of alkenes & alkynes B. Electrophilic Additions to Alkynes 1. Hydrohalogenation (Chapter 7) 2. Halogenation 3. Halohydrins 4. Hydration

Alkenes & Alkynes II. Reactions of alkenes & alkynes B. Electrophilic Additions to Alkynes 3. Halohydrins

Alkenes & Alkynes II. Reactions of alkenes & alkynes B. Electrophilic Additions to Alkynes 4. Hydration i. acid catalyzed

Alkenes & Alkynes II. Reactions of alkenes & alkynes B. Electrophilic Additions to Alkynes 4. Hydration ii. oxymercuration

Alkenes & Alkynes II. Reactions of alkenes & alkynes B. Electrophilic Additions to Alkynes 4. Hydration ii. Hydroboratoin & oxidation

Alkenes & Alkynes II. Reactions of alkenes & alkynes C. Reductions 1. Alkenes i. Catalytic hydrogenation

Alkenes & Alkynes II. Reactions of alkenes & alkynes C. Reductions 2. Alkynes i. Catalytic hydrogenation a. Complete reduction

Alkenes & Alkynes II. Reactions of alkenes & alkynes C. Reductions 2. Alkynes i. Catalytic hydrogenation ii. Lindlar’s catalyst (partial reduction)

Alkenes & Alkynes II. Reactions of alkenes & alkynes C. Reductions 2. Alkynes iii. Dissolving metal reduction (partial reduction)

ep ep !

Alkenes & Alkynes II. Reactions of alkenes & alkynes D. Alkyne alkylation

Fig. 8 -19, p. 292

Alkenes & Alkynes II. Reactions of alkenes & alkynes E. Carbene addition

Fig. 7 -6, p. 228

Carbenes

Alkenes & Alkynes II. Reactions of alkenes & alkynes F. Oxidations Introduction

Alkenes & Alkynes II. Reactions of alkenes & alkynes E. Oxidations 1. epoxidation i. Peracids (RCO 3 H)

Epoxide formation through reaction of peracids

Alkenes & Alkynes II. Reactions of alkenes & alkynes F. Oxidations 1. epoxidation ii. via halohydrins

The Nobel Prize in Chemistry 2001 "for their work on chirally catalysed hydrogenation reactions" William S. Knowles Ryoji Noyori "for his work on chirally catalysed oxidation reactions" K. Barry Sharpless

Thalidomide Ø Racemic thalidomide prescribed for morning sickness (1956 – 1961) Ø (R)-enantiomer is an antiemetic Ø (S)-enantiomer is a teratogen

Sharpless epoxidation (CH 3)3 COOH

Knowles Asymmetric Reduction

Alkenes & Alkynes II. Reactions of alkenes & alkynes F. Oxidations 2. dihydroxylation i. osmium tetraoxide

Alkenes & Alkynes II. Reactions of alkenes & alkynes E. Oxidations 2. dihydroxylation ii. from epoxides

Alkenes & Alkynes II. Reactions of alkenes & alkynes F. Oxidations 2. Dihydroxylation Application : Synthesis

Alkenes & Alkynes II. Reactions of alkenes & alkynes E. Oxidations 3. oxidative cleavage i. ozonolysis

p. 237

Alkenes & Alkynes II. Reactions of alkenes & alkynes E. Oxidations 3. oxidative cleavage i. ozonolysis

Alkenes & Alkynes II. Reactions of alkenes & alkynes F. Oxidations 3. oxidative cleavage ii. permanganate

Alkenes & Alkynes II. Reactions of alkenes & alkynes F. Oxidations 3. oxidative cleavage iii. from diols

Alkenes & Alkynes II. Reactions of alkenes & alkynes G. Conjugated Dienes Introduction

Fig. 8 -12, p. 281

Fig. 8 -13, p. 282

Fig. 8 -14, p. 282

Alkenes & Alkynes II. Reactions of alkenes & alkynes G. Conjugated Dienes 1. Addition of HX

Reaction energy diagram for addition of HBr to butadiene

Alkenes & Alkynes II. Reactions of alkenes & alkynes G. Conjugated Dienes 2. The Diels-Alder reaction Introduction a. the overall reaction b. history c. nature of the diene and dienophile d. the molecular orbital picture e. conformation of the diene

Alkenes & Alkynes II. Reactions of alkenes & alkynes F. Conjugated Dienes 2. The Diels-Alder reaction Introduction a. the overall reaction

Alkenes & Alkynes II. Reactions of alkenes & alkynes G. Conjugated Dienes 2. The Diels-Alder reaction Introduction b. history Albrecht reaction Liebigs 1906, 348, 31. Staudinger, H. ; Bruson, H. A. Liebigs 1926 , 446 , 97. Diels, O. ; Alder, K. Liebigs. 1928, 460, 98. Nobel Prize 1950

The Nobel Prize in Chemistry 1950 "for their discovery and development of the diene synthesis " Otto Paul Hermann Diels Kurt Alder

Alkenes & Alkynes II. Reactions of alkenes & alkynes G. Conjugated Dienes 2. The Diels-Alder reaction Introduction c. nature of the diene and dienophile

p. 286

Alkenes & Alkynes II. Reactions of alkenes & alkynes F. Conjugated Dienes 2. The Diels-Alder reaction Introduction d. the molecular orbital picture

Alkenes & Alkynes II. Reactions of alkenes & alkynes F. Conjugated Dienes 2. The Diels-Alder reaction Introduction e. the diene conformation

Alkenes & Alkynes II. Reactions of alkenes & alkynes F. Conjugated Dienes 2. The Diels-Alder reaction Stereochemistry (Alder’s Endo Rule)

Alkenes & Alkynes II. Reactions of alkenes & alkynes F. Conjugated Dienes 2. The Diels-Alder reaction Regiochemistry (The Ortho Rule)

Alkenes & Alkynes II. Reactions of alkenes & alkynes F. Conjugated Dienes 2. The Diels-Alder reaction Regiochemistry (The Para Rule)

Fig. 8 -17, p. 287