Substitution Workshop

SN2
Explain how the rates of SN2 reactions are affected by

- Strength of nucleophile/solvent

Polar protic solvents stabilize charged species (ions). Reactants (nucleophiles) are typically charged in
SN2 reactions. A polar protic solvent will form ion-dipole bonds to the nucleophile (stabilizing effect).
The smaller the nucleophile, the greater the stabilization via the solvent. So, in protic solvents, the
larger nucleophile is the stronger nucleophile.

In aprotic solvents, no such effect exists. Therefore, in aprotic solvents, the strongest base is the
strongest nucleophile.

- Leaving group

The leaving group is a product of the reaction. The more stable the product, the more favorable the
reaction. The more stable the leaving group, the faster the SN2 reaction

- Substrate (R-X. 1° vs 2° vs 3°)

The rate determining step involves the nucleophile approaching the substrate (R-X). The easier it is for
the nuclephile to approach the site of substitution, the faster the reaction. So a less hindered substrate
(1°) will react faster than a more hindered substrate (2°)

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Explain the stereochemistry of an SN2 reaction

Draw the 3D mechanism (Leaving group in the plane) for (S) 2-iodobutane + Sodium Cyanide.

Inversion of stereochemistry is observed at the site of the substitution. The nucleophile approaches
from the opposite side of the leaving group (backside attack)
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Draw the 3D mechanism (chair conformation) for cis-1-bromo-4-methylcyclohexane + sodium

methoxide

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SN1
What is the primary factor affecting the rate of an SN1 reaction?

The rate determining step is the formation of the carbocation. The more stable the carbocation, the
faster the SN1

Explain the stereochemistry of an SN1 reaction

The leaving group leaves resulting in a carbocation (planar, sp2 hybridized). The nucleophile can attach
for either face with equal probability resulting in both inversion and retention of stereochemistry if the
site of substitution is asymmetrical.
Draw the 3D mechanism for the following:

O
Br
Methanol
racemic
 O
I Ethanol O

H H H
Draw mechanisms which explain the following:

I O R O R
ROH
+
I O R O R
ROH
+
I

ROH R
O
 R
Br O
ROH