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SN1 Reaction SN2 Reaction SN1 vs.

SN2 Summary

Stereochemistry Stereochemistry SN1 SN2


Substitution occurs with a mixture of retention and inversion at a Substitution occurs with inversion of configuration at chiral centers
stereocenter
Br CN
Bonds Bonds Rate Law Unimolecular Bimolecular
Br HO OH Na C N Formed Broken (substrate only) (substrate and nucleophile)
H 2O + Na Br
3 1 3 1 3 1
4 2 4 2 C2 CN C2 Br
+ H 3O Br 3 1 3 1
2 2 2
One stereoisomer One stereoisomer "Big Barrier" Carbocation Steric hindrance
stability
inversion!
retention inversion
This substitution reaction results in an inversion of configuration at C-2
Alkyl halide
(electrophile) 3 > 2 >>1 1 > 2 >>3
Rate Law Rate Law (fastest) (fastest)
The rate of the reaction is ONLY sensitive to the concentration of The rate of the reaction is sensitive to the concentration of the
the substrate (and not the nucleophile) substrate AND the nucleophile
Nucleophile Weak (generally Strong (generally
Br HO Br CN
H 2O Na C N neutral) bearing a negative
4 2 4 2 + H 3O Br Rate = k [RBr] 4 2 4 2 + NaBr Rate = k [RBr] [ CN] charge)
3 1 3 1 3 1 3 1

Solvent Polar protic Polar aprotic


(e.g. alcohols) (e.g. DMSO, acetone)
Rate Rate Rate Rate

(doubling the (doubling the


Stereochemistry Mix of retention Inversion
1 2 3 4 1 2 3 4 concentration of 1 2 3 4 1 2 3 4 concentration of and inversion
] water has no [ Br ] [ :CN ] CN doubles the rate)
[ [ H 2O ]
Br effect on the rate)

Substrate Substrate Comparing SN1 vs. SN2 reactions


The key skill to start with is identifying the leaving group
Fastest for tertiary, slowest for primary Slowest for tertiary, fastest for primary (methyl even faster) Look for halogens (Cl, Br, I) or tosylates/mesylates (OTs, OMs)
Rate Br NC
Rate Alternatively, look for alcohols (OH) if acid is present
Br HO Na C N
H 2O 1.2 10 6
Tertiary
2 2 < 0.001
Tertiary + H 3O Br 4
3 1
4
3 1 Once you've identified the leaving group, instpect the carbon it is
2 2
3 1 50C 3 1 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
Br CN no attached carbons, that's the special case of "methyl" (SN 2 for sure!)
Na C N 1
Br OH Secondary
H 2O 2 2 If the carbon is tertiary, it's likely SN1. You can rule out SN 2 due to steric
Secondary + H 3O Br 11.6 4
3 1
4
3 1
hindrance.
2 2
3 1 50C 3 1 If the carbon is primary, it's likely SN 2. You can rule out SN1 due to the fact that
Na C N primary carbocations are unstable [one exception: resonance stabilized
Primary Br CN ~20 carbocations].
Br OH 4 2 4 2
H 2O 1 3 1 3 1
Primary + H 3O Br
1 1 Next, examine the nucleophile. A negatively charged nucleophile
2 50C 2
Na C N generally indicates an SN 2 reaction. A neutral nucleophile (such as
(likely occuring through SN 2 mechanism) Methyl Br CN ~1000 H 2O or ROH) generally indicates an SN1 reaction.
H 3C H 3C
From "March's Advanced Organic Chemistry", 5th Ed. p. 431 1
Finally, check the solvent. A polar aprotic solvent (such as DMSO,
acetone, acetonitrile, or DMF) generally indicates SN 2, whereas a
Mechanism H
1
Step 1: Loss of
Mechanism polar protic solvent such as H 2O or ROH generally indicates SN1
Br leaving group (slow) One step (backside attack) conditions.
Stepwise - leaving group 2
3
leaves (slow) forming a In the "backside attack", the nucleophile attacks the substrate from the backside
(S) alkyl halide
carbocation, which is then 4
in a single step, resulting in inversion of configuration.
attacked by a nucleophile
(fast)
H
1
H
+
H 1 If you found this useful, click here
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Br 1 H N C Br N C Br N C
H H 2 2
3
1 Path A 3

H 2O 2
OH 2 3
2 OH 2 4
partial bonds!
4
chemistry cheat sheets !
3
Path B 4
(S) (S) (R)
(R) OH 2 Transition state
4
Carbocation
H H Explains bimolecular rate law (depends on conc. of nucleophile and substrate)
Step 3: Step 2: Attack of nucleophile Step 3: Explains inversion of stereochemistry
deprotonation on carbocation (fast) deprotonation Explains sensitivity to steric hindrance (bulky groups slow down backside attack)
Can occur from either side of
H 1 the flat carbocation 1 H This is called the SN2 mechanism
(Path A or Path B) (Substitution, Nucleophilic, bimolecular)
HO 2 2 OH
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3 3

(R) 4 4 (S) Questions, comments? james@masterorganicchemistry.com


Path A gives inversion (R) Path B gives retention (S)