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p. 251. Alkenes & Alkynes. Prepapration of alkenes 1. Dehydrohalogenation 2. Dehydration. Alkenes & Alkynes. Reactions of alkenes & alkynes A. Electrophilic Additions Hydrohalogenation i. alkenes ii. alkynes 2. Halogenation i. alkenes ii. alkynes Halohydrins i. alkenes
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Alkenes & Alkynes • Prepapration of alkenes • 1. Dehydrohalogenation • 2. Dehydration
Alkenes & Alkynes • Reactions of alkenes & alkynes • A. Electrophilic Additions • Hydrohalogenation • i. alkenes • ii. alkynes • 2. Halogenation • i. alkenes • ii. alkynes • Halohydrins • i. alkenes • ii. alkynes • 4. Hydration • i. alkenes • ii. alkynes
Alkenes & Alkynes • Reactions of alkenes & alkynes • A. Electrophilic Additions • Hydrohalogenation • i. alkenes • ii. alkynes
Alkenes & Alkynes • Reactions of alkenes & alkynes • A. Electrophilic Additions • 2. Halogenation • i. alkenes (working backwards)
Alkenes & Alkynes • Reactions of alkenes & alkynes • A. Electrophilic Additions • Halohydrins • i. alkenes
Alkenes & Alkynes • Reactions of alkenes & alkynes • A. Electrophilic Additions • Halohydrins • ii. alkynes
Alkenes & Alkynes • Reactions of alkenes & alkynes • A. Electrophilic Additions • 4. Hydration • i. alkenes • a. acid catalyzed
Alkenes & Alkynes • Reactions of alkenes & alkynes • A. Electrophilic Additions • 4. Hydration • i. alkenes • a. hydroboration & oxidation
+ + - - d d d d Fig. 7-4, p. 225
Alkenes & Alkynes • Reactions of alkenes & alkynes • A. Electrophilic Additions • 4. Hydration • i. alkynes • a. acid catalyzed
Alkenes & Alkynes • Reactions of alkenes & alkynes • A. Electrophilic Additions • 4. Hydration • i. alkynes • b. oxymercuration
Alkenes & Alkynes • Reactions of alkenes & alkynes • A. Electrophilic Additions • 4. Hydration • i. alkynes • a. hydroboration & oxidation
Alkenes & Alkynes • Reactions of alkenes & alkynes • B. Reductions • 1. Alkenes • i. Catalytic hydrogenation
Alkenes & Alkynes • Reactions of alkenes & alkynes • B. Reductions • 1. Alkynes • i. Catalytic hydrogenation • a. Complete reduction
Alkenes & Alkynes • Reactions of alkenes & alkynes • B. Reductions • 1. Alkynes • i. Catalytic hydrogenation • b. Lindlar’s catalyst (partial reduction)
Alkenes & Alkynes • Reactions of alkenes & alkynes • C. Reductions • 1. Alkynes • ii. Dissolving metal reduction (partial reduction)
Alkenes & Alkynes • Reactions of alkenes & alkynes • C. Alkyne alkylation
Alkenes & Alkynes • Reactions of alkenes & alkynes • D. Carbene addition
Alkenes & Alkynes • Reactions of alkenes & alkynes • E. Oxidations • Introduction
Alkenes & Alkynes • Reactions of alkenes & alkynes • E. Oxidations • 1. epoxidation • Peracids (RCO3H)
Alkenes & Alkynes • Reactions of alkenes & alkynes • E. Oxidations • 1. epoxidation • ii. via halohydrins
The Nobel Prize in Chemistry 2001 "for their work on chirally catalysed hydrogenation reactions" "for his work on chirally catalysed oxidation reactions" William S. Knowles Ryoji Noyori K. Barry Sharpless
Thalidomide • Racemic thalidomide prescribed for morning sickness (1956 – 1961) • (R)-enantiomer is an antiemetic • (S)-enantiomer is a teratogen
Sharpless epoxidation (CH3)3COOH
Alkenes & Alkynes • Reactions of alkenes & alkynes • E. Oxidations • 2. dihydroxylation • i. osmium tetraoxide
Alkenes & Alkynes • Reactions of alkenes & alkynes • E. Oxidations • 2. dihydroxylation • ii. from epoxides
Alkenes & Alkynes • Reactions of alkenes & alkynes • E. Oxidations • 2. Dihydroxylation • Application : Synthesis
Alkenes & Alkynes • Reactions of alkenes & alkynes • E. Oxidations • 3. oxidative cleavage • i. ozonolysis
Alkenes & Alkynes • Reactions of alkenes & alkynes • E. Oxidations • 3. oxidative cleavage • i. ozonolysis
Alkenes & Alkynes • Reactions of alkenes & alkynes • E. Oxidations • 3. oxidative cleavage • ii. permanganate
Alkenes & Alkynes • Reactions of alkenes & alkynes • E. Oxidations • 3. oxidative cleavage • iii. from diols
Alkenes & Alkynes • Reactions of alkenes & alkynes • F. Conjugated Dienes • Introduction
Alkenes & Alkynes • Reactions of alkenes & alkynes • F. Conjugated Dienes • 1. Addition of HX