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SN1 Reaction

SN2 Reaction

Stereochemistry

Substitution occurs with a mixture of retention and inversion at a


stereocenter
Br

HO

H 2O

retention

Rate = k [RBr]

+ H 3O Br

Br

(doubling the
concentration of
water has no
effect on the rate)

H 2O ]

Fastest for tertiary, slowest for primary

Tertiary

50C

Br

Secondary

50C

1
3
4

Step 3:
deprotonation

H
HO

3
4

Path A
OH 2

Stepwise - leaving group


leaves (slow) forming a
carbocation, which is then
attacked by a nucleophile
(fast)

H 2O 2
(R)

1.2 10 6

11.6

+ H 3O Br

+ H 3O Br

(likely occuring through SN 2 mechanism)


From "March's Advanced Organic Chemistry", 5th Ed. p. 431

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

The rate of the reaction is sensitive to the concentration of the


substrate AND the nucleophile
Br

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)

Path B gives retention (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

Comparing SN1 vs. SN2 reactions

Slowest for tertiary, fastest for primary (methyl even faster)


Br

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

The key skill to start with is identifying the leaving group


Look for halogens (Cl, Br, I) or tosylates/mesylates (OTs, OMs)
Alternatively, look for alcohols (OH) if acid is present
Once you've identified the leaving group, instpect the carbon it is
attached to. How many carbons is that carbon connected to? That
will tell you if the carbon is primary, secondary, or tertiary. If there are
no attached carbons, that's the special case of "methyl" (SN 2 for sure!)

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

Next, examine the nucleophile. A negatively charged nucleophile


generally indicates an SN 2 reaction. A neutral nucleophile (such as
H 2O or ROH) generally indicates an SN1 reaction.

H 3C

N C

Rate Law

CN]

Finally, check the solvent. A polar aprotic solvent (such as DMSO,


acetone, acetonitrile, or DMF) generally indicates SN 2, whereas a
polar protic solvent such as H 2O or ROH generally indicates SN1
conditions.

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

One step (backside attack)

(S) alkyl halide

Carbocation

4
(R)
Path A gives inversion (R)

Br

+ Na

Mechanism

Step 1: Loss of
leaving group (slow)

Step 2: Attack of nucleophile


on carbocation (fast)
Can occur from either side of
the flat carbocation
(Path A or Path B)

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

The rate of the reaction is ONLY sensitive to the concentration of


the substrate (and not the nucleophile)
H 2O

Br

+ H 3O Br

Rate Law
Br

Stereochemistry
Substitution occurs with inversion of configuration at chiral centers

OH
3

SN1 vs. SN2 Summary

N C

+
Br

partial bonds!

Transition state

H
N C

1
3
4

(R)

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Explains bimolecular rate law (depends on conc. of nucleophile and substrate)


Explains inversion of stereochemistry
Explains sensitivity to steric hindrance (bulky groups slow down backside attack)

This is called the SN2 mechanism


(Substitution, Nucleophilic, bimolecular)

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