mechanismer

Alkenes and Addition Reactions

T
wer =C

Addition Reactions - General Characteristics T

-
• Addition of A-B across double bond (H-X, H-OH, X-X, etc.)

•  electrons in C=C typically behave as nucleophile

Hydrohalogenation (addition of H-X)

• Mechanism – addition of H+ followed by nucleophilic attack by X-

• Markovnikov addition, rearrangements possible

Sp2

x
c H
Sp3
* *

“Markovnikov” Rule

• In mechanisms with carbocations, the most stable carbocation is generated (don't havae
• For HX addition, this results in X- adding to most substituted C atom
T
# *
Th It
1,2-hydride or alkyl shifts

• Carbocations often rearrange to form a more stable carbocation (1o to 2o/3o, 2o to 3o)

• 1,2 shifts are common (hydride OR alkyl shift)

For
~ To
o ↓
B
Hydration (addition of H2O)

• Acid catalyzed (“dilute” H2SO4)

• Mechanism – addition of H+ followed by nucleophilic attack by H2O

• Markovnikov addition, rearrangements possible

-H
=>
H
Cat .

JHz

Z ·
most
sub

-
? K
H2SO4
Ti Fo a
It
① ⑳

T
⑪ ⑤

EY IV
Hydroboration – alternative hydration reaction (BH3THF or B2H6)

• Mechanism - concerted; 4-member ring TS

ends up
160 tothee sub
• anti-Markovnikov product, syn-addition -

on same
side
H OH

-
i T H
# BH2
(hastobemi LON
*
-

7
H

-
2

# #it

B⑰ H
BHz ⑪ Syn
Free Radical Addition of HBr (with ROOR)

• Mechanism – anti-Markovnikov addition of HBr (Br on least subst. C atom), RO-OR

generates radical initiator

N
: OR alkoxy radical
2
&
& next weenest bond

Iv Bro + ROH
&
# next weakest
-v
Bri
·
W
B

HBR Br
-
ROOR
Addition of X2

• Mechanism – formation of halonium ion, opposite face attack by X-

• anti-addition of X2 (Cl2 or Br2) across double bond

Halohydrin Formation (addition of X2 in H2O)

• Mechanism – formation of halonium ion, opposite face attack by H2O

• anti-addition of X2 in the presence of water, generates halohydrin

Hydrogenation (H2, metal)

• syn-addition of H2 across double bond, generates alkane (reduction of C=C)

• Heterogenous catalysis, H2 and alkene adsorbed to surface of metal (Pt common)

Epoxidation

• Synthesis - peroxy acids (peracetic acid or mCPBA), syn-addition

• Concerted mechanism generates epoxide and carboxylic acid

O R
C C R
C O
O C
O
C O
H C
OH
alkene peroxy acid epoxide carboxylic acid

O R
C C
O
C H O
Ozonolysis

• Addition to alkene (molozinide) followed by C=C bond cleavage

• Generates ketones or aldehydes in the presence of Zn or S(CH3)2

Synthesis Examples