SN2 Reaction
Stereochemistry
HO
H 2O
retention
Rate = k [RBr]
+ H 3O Br
Br
(doubling the
concentration of
water has no
effect on the rate)
H 2O ]
Tertiary
50C
Br
Secondary
50C
1
3
4
Step 3:
deprotonation
H
HO
3
4
Path A
OH 2
H 2O 2
(R)
1.2 10 6
11.6
+ H 3O Br
+ H 3O Br
Mechanism
OH
H 2O
2
Rate
+ H 3O Br
OH
50C
H 2O
Br
Primary
HO
H 2O
Br
Bonds
Broken
C2 Br
C2 CN
One stereoisomer
CN
C N
Na
Rate = k [RBr] [
+ NaBr
OH 2
Path B
OH 2
(S)
H
Step 3:
deprotonation
1
3
4
H
2
OH
(S)
"Big Barrier"
Br
(doubling the
concentration of
CN doubles the rate)
[ :CN ]
Unimolecular
Bimolecular
(substrate only) (substrate and nucleophile)
Carbocation
stability
3 > 2 >>1
(fastest)
Steric hindrance
1 > 2 >>3
(fastest)
Weak (generally
neutral)
Strong (generally
bearing a negative
charge)
Solvent
Polar protic
(e.g. alcohols)
Polar aprotic
(e.g. DMSO, acetone)
Stereochemistry
Mix of retention
and inversion
Inversion
Tertiary
Na
Methyl
H 3C
NC
C N
Br
Secondary
Primary
SN2
Nucleophile
Rate
Na
Br
Br
Na
Na
C N
C N
Rate
< 0.001
CN
C N
H
3
(S)
Br
CN
~20
If the carbon is tertiary, it's likely SN1. You can rule out SN 2 due to steric
hindrance.
If the carbon is primary, it's likely SN 2. You can rule out SN1 due to the fact that
primary carbocations are unstable [one exception: resonance stabilized
carbocations].
CN
~1000
H 3C
N C
Rate Law
CN]
In the "backside attack", the nucleophile attacks the substrate from the backside
in a single step, resulting in inversion of configuration.
Br
SN1
Alkyl halide
(electrophile)
Rate Law
Carbocation
4
(R)
Path A gives inversion (R)
Br
+ Na
Mechanism
Step 1: Loss of
leaving group (slow)
Substrate
Substrate
Br
Rate
Rate
Rate
Bonds
Formed
CN
C N
Na
One stereoisomer
inversion
HO
inversion!
This substitution reaction results in an inversion of configuration at C-2
Br
+ H 3O Br
Rate Law
Br
Stereochemistry
Substitution occurs with inversion of configuration at chiral centers
OH
3
N C
+
Br
partial bonds!
Transition state
H
N C
1
3
4
(R)