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Module 2.3 Neighbouring Group Participation; SN1 vs SN2

Objectives:

At the end of this module, learners will be able to

• Identify if a given reaction is proceeding through NGP.

• Compare the rates of reaction proceeding through NGP and without NGP.
• Predict the mechanism and stereochemical outcome of a given reaction based on
the reaction conditions.
• Classify a given reaction as SN1, SN2 or proceeding through NGP based on the
stereochemical outcome and kinetics data.
Contents:
2.3.1 Introduction
2.3.2 Neighbouring Group participation
2.3.3 SN1 vs SN2

2.3.1 Introduction
In module 2.1, we discussed the SN2 mechanism, which is bimolecular, single step and
resulting in inversion of configuration. However, there are certain molecules, which show
enhanced rate of reaction under SN2 reaction conditions and proceed with retention of
configuration. This module will look at these types of reactions.

2.3.2 Neighbouring Group Participation (NGP)

If one were to compare the solvolysis of chloro cyclooctane (A) and 5-chloro oxa
cyclooctane (B), it is found that B reacts almost 5x104 times faster than A. This can be
explained by the involvement of the lone pairs of electrons on the oxygen, which facilitates
the departure of the leaving group Cl- by an intramolecular SN2 mechanism. This results in
formation of the intermediate oxonium ion C, which is then attacked by the weak
nucleophile water to yield the product after loss of a proton. In case of A, it is a simple SN2
mechanism operating. NGP is also referred to as anchimeric assistance. As two SN2 reactions
are involved, the net reaction in case the substrate is chiral, is retention of configuration.

H-OH
OH
X

SN2
-H+

X OH

H-OH
Intramolecular SN2 SN2

O + -H+
O O
B
C

Prof. Lakshmy Ravishankar UNESCO OER4BW

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2.3.3 SN1 vs SN2

In predicting whether the reaction will proceed by a SN1 or SN2 reaction, three factors have
to be considered, viz. i) the substrate -whether it is methyl, 10, 20, 30, allylic, benzylic, vinyl
or phenyl ii) the strength of the nucleophile and 3) the solvent.

i) Substrate: the substrates which can yield a stable carbocation will proceed by an SN1
mechanism, while the substrates like methyl and 10 which are least hindered will proceed by
a SN2 mechanism. The 20 halides can undergo either SN1 or SN2 reactions depending on the
reaction condition i.e the nucleophile and solvent. A strong nucleophile in a polar aprotic
solvent will favour a SN2 mechanism, while a weak nucleophile in a polar protic solvent will
favour the SN1 mechanism.

Possible halide structure Substitution reaction

Methyl or primary SN2
Secondary SN1 or SN2
Tertiary SN1
Primary Allylic or benzylic SN1 or SN2
Tertiary allylic or benzylic SN1
Vinylic ( CH2=CHCl or Aryl C6H5Cl) Neither SN1 or SN2

ii) Nucleophile: powerful nucleophiles, especially those with negative charges, favour the
SN2 mechanism. Weaker nucleophiles such as water or alcohols favour the SN1 mechanism.

iii) Solvent: Polar aprotic solvents favor the SN2 mechanism by enhancing the reactivity of
the nucleophile. Polar protic solvents favor the SN1 mechanism by stabilizing the transition
state and carbocation intermediate. SN1 reactions are called solvolysis reactions when the
solvent is the nucleophile.

2.3.3.1 Comparison between SN1 and SN2 reactions

Reaction Parameter SN1 SN2
Alkyl halide 30 > 20 > >>10 > Methyl Methyl>10 >20 >>> 30
Nucleophile Weak nucleophile (often the Strong with high
solvent) concentration
Mechanism two steps Single step
R.D.S. Formation of carbocation Formation of bimolecular
T.S.
Rate law Rate =k [RX] Rate= k [RX][Nu-]
Solvent Polar Protic Polar aprotic
Stereochemistry Partial racemization with 100% inversion
slightly greater inversion
product

Prof. Lakshmy Ravishankar UNESCO OER4BW

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For eg. Consider the following reaction. As the substrate is a 30 halide and the solvent is a
polar protic solvent which is also a weak nucleophile we can say that the reaction proceeds
by a SN1 mechanism resulting in partial racemization.

OH
Br
H-OH OH
+

If the solvent was a polar aprotic solvent and the nucleophile was a strong nucleophile, then
the reaction pathway would follow an SN2 mechanism as shown in the following example.
Br H OH
H HO-

DMSO

So far we have seen three classes of nucleophilic substitution reaction. A fourth class the S Ni
(Substitution Nucleophilic Internal) will be discussed in the next module 2.4

Prof. Lakshmy Ravishankar UNESCO OER4BW