LMZ/CHEM109A/ Winter 2010

Chapters 4: Reactions of alkenes I. Electrophilic Addition reactions e.g.

H H H C C CH3

- why the regioselectivity? -- lower activiation energy

+ + H Br

1st step

H H C H

C H + Br CH3

2nd step

H H C H

Br C H CH3

A. Electrophilic addition of H-X to alkenes (sec. 4.1) - Regioselectivity Bell-Evans-Polani principle: in a series of closely related reactions, Ea is proportional to H or G. - Markovnikovs rule: In the ionic addition of an unsymmetrical reagent to a double bond, the positive portion of the adding reagent attaches itself to a carbon atom of the double bond so as to yield the more stable carbocation as an intermediate.

- carbocation stability
B. Addition of water (Hydration of alkenes and alkynes) and addition of alcohol

1. Acid catalyzed hydration of alkene (Sec. 4.5)

- Hammond postulate: transition state is more similar in structure to the species to which it is more similar to energy

a. mechanism:

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b. Regiochemistry: Markovnikovs type H on ______ substituted carbon (generate more stable carbocation), OH on ________ substituted carbon c. Stereochemistry: __________________________________ 2. Addition of alcohols e.g. Regiochemistry: X on less substituted C, OH on more substituted carbon C. Carbocation rearrangement via 1,2-shifts: form more stable carbocation (sec. 4.6) Stereochemistry:________________________________________ F. Oxymercuration-demercuration (Markovnikovs addition of water to alkenes) (Sec. 4.8)
a. e.g. 1. Hg(OAc)2, H2O/THF O - OAc = O C CH 2. NaBH4

HO
3

H
(Regiochemistry: Markovnikov's type)

b. mechanism:

D. Electrophilic addition of X2 to alkenes (Sec. 4.7) i. General equation

R H H H + X2 R H X X H H

ii. Proposal of halonium ion by George Kimball and Irving Roberts in 1937
+ X R H H H R H X H H

Halonium ion
X X R H X X H H

II. Epoxidation of alkene (sec. 4.9)

iii. Stereochemistry: ___________________________ E. Halohydrin formation (sec. 8.9)

R H H H + X2 + H 2 O R X H H HO H halohydrin

Mechanism:

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III. Hydroboration of Alkenes and oxidation: (H. C. Brown, Nobel Prize in 1979) (Sec. 4.10)

c). reactions:
H 2, PtO2, H+ ??

b. mechanism:

or H 2, Pd/C

IV. Catalytic Hydrogenation of Alkenes: (Sec. 4.11) a) Catalysts: Ni, Pd; Pt; Pd/C; Rh[(C6H5)3P]Cl, or Lindlar catalyst (Industrial application: vegetable oil to margarine)

Stereochemistry: mainly syn- addition from the less hindered side

b) Examples b) a way to interrogate C-C double bond strength/alkene stability

e.g.,