Organic Chemistry Nucleophilic Substitution and Elimination Reactions (SN1, SN2, E1, E2)

SN1 SN2 E1 E2

Stepwise reaction in which one Stepwise: two bonds are cleaved from Single, concerted step in which
Single, concerted step in which one
substituent replaces another. adjacent positions to form a π–bond. substituents are eliminated & double
substituent replaces another.
Summary 1. Formation of carbocation 1. Formation of carbocation bond is formed simultaneously.
Nuᶱ–C partially formed, C–X partially
2. Attack by nucleophile to form 2. Removal of adjacent hydrogen to Hydrogen is removed and double
broken (transition state theory)
substituted product form double bond bond is formed

3° > 2° ≫ 1° 1° > 2° ≫ 3° 3° > 2° ≫ 1° 3° > 2° > 1°

Substrate
Also on benzyllic or aryllic Methyl = always 3° preferred Highly substituted alkene formed**

First-order Second-order First-order Second-order

Rate
R = k [substrate] R = k [Nuᶱ] [substrate] R = k [substrate] R = k [base] [substrate]

Strong Nuᶱ Strong base for 2° & 3°

Weak Nuᶱ Weak base
(Lewis bases) e.g.: OH– & RO–
Nucleophile e.g.: H2O, CH3OH, and CH3CH2OH e.g.: H2O, CH3OH, and CH3CH2OH
(Nuᶱ) e.g.: R–SH, NaOCH3, LiCH3, NaOH, Strong, bulky base for 1°
Nuᶱ  unimportant High temperature
NaCN, KCN, NaNH2, LiBr, KI, NaSMe e.g.: t-BuOK

Polar, protic Polar, aprotic Polar, protic Polar, aprotic

(If reactant is not charged) (If reactant is not charged)
Solvent e.g.: DMF, DMSO, acetone, CH2Cl2, e.g.: DMF, DMSO, acetone, CH2Cl2,
e.g.: alcohols (CH3OH), water ethers (R–O–R’) e.g.: alcohols (CH3OH), water ethers (R–O–R’)

Requires good leaving group Requires good leaving group β–Elimination β–Elimination
i.e. a weak base i.e. a weak base
Leaving Group
Eliminates 1 equivalent acid to form Eliminates 1 equivalent acid to form
TsO– , MsO–, I–, Br–, Cl–, H2O, NH3 TsO– , MsO–, I–, Br–, Cl–, H2O, NH3 alkene alkene

Racemic mixture (50:50 R & S)

Rearrangement possible Inversion Syn or Anti
Bulkiest groups on opposite sides
Stereochemistry (Carbocation is trigonal planar with Rearrangement rare E, Z
Rearrangement likely
empty p-orbital  attack can happen R becomes S and S becomes R Rearrangement rare
from top or bottom)

Mechanism

There is competition between SN1 and E1 as well as SN2 and E2. As a result, there will often be a major and minor product.