SN1 – Unimolecular Nucleophilic Substitution

Mechanism:
1. Leaving group removal (forms carbocation)
2. Rearrangement (if applicable, see below)
3. Nucleophilic attack (remember many times your oxygen will become + charged)
4. Deprotonation (bond from H will attack an atom to form lone pair)

**Ph is a phenyl substituent, doesn’t have any significance to the reaction**

NOTE:
 “Neutral nucleophiles will lose a hydrogen.”
 If electrophilic carbon is directly bonded to a 3° or 4°carbon, rearrangement will occur. 3° will
result in H (hydride) shift, while 4° will result in an alkyl shift.
o H or CH3 will “jump” to the adjacent carbon, moving the carbocation (+ charge) to a
more stable state (greater number of alkyl groups attached to the carbocation increases
stability).
 Products formed will be a racemic mixture.
o Beginning with a reactant which is cis will yield both cis and trans products.
 The same goes for R and S, starting with one yields both.
o Many times, you will have multiple products as your final solution.
 SN1 reaction is favored by polar protic solvents & weak nucleophiles (H2O or alcohols).
 E1 and SN1 mechanisms linked due to carbocation intermediate

SN2 – Bimolecular Nucleophilic Substitution

Mechanism (concerted):
1. Leaving group removal, nucleophilic attack; occurs simultaneously

NOTE:
 One step mechanism.
 Products formed will have inverted stereochemistry.
o Beginning with a reactant determined to have ‘R’ stereochemistry will yield ONLY S
products.
 Likewise, for cis and trans; beginning with cis will produce a trans product.
 SN2 reaction is slowed by steric hindrance
o 3°<2°<1°<Methyl
 SN2 reaction is favored by polar aprotic solvents.
  Will yield one final product

E1 – Unimolecular Elimination
Mechanism:
1. Leaving group removal (forms carbocation)
2. Alkene formation

NOTE:
 In the second step, the bond from a hydrogen on an ADJACENT carbon will snap down to form
the alkene product.
 Follows Zaitsev’s rule
o The more substituted alkene will be the predominant product. This really means: which
double bond has more carbons directly bonded to it? That will be your most stable bond,
resulting in your product favoring that configuration.
 Sometimes there are multiple adjacent carbons containing hydrogen, each of these forms a new
product.
 Overall, can yield one or more products depending on above statement.
 E1 and SN1 mechanisms linked due to carbocation intermediate

E2 – Bimolecular Elimination
Mechanism (concerted):
1. Leaving group removal, alkene formation; occurs simultaneously.

NOTE:
 Also follows Zaitsev’s rule (see E1).
 The adjacent hydrogen which will be removed to form the alkene, and the leaving group must
have the correct orientation to occur.
o Must be in ANTI position (trans, 180° dihedral angle, axial (in rings)).
 Look to ALL adjacent carbons for correctly oriented hydrogens
o May be occupied by another substituent, meaning this is not eligible for removal.
 Requires strong base to occur.
o Hydroxide (-O-H) and alkoxide (-O-R) are strong bases.
 o Strong bases are also good nucleophiles, so pay close attention what type of carbon
you’re dealing with. Remember, a 3° carbon will never produce an SN2 reaction due to
steric hindrance. If faced with that situation, the reaction will undergo E2.
 May form one or more products, dependent upon positioning of hydrogens on adjacent carbons.
 For both E1 and E2 stability of products (predominant product formed) is as follows:
o Conjugated double bonds (two double bonds separated by a single bond) > number of
alkyl groups attached directly to the alkene > cis/trans (trans favored due to lack of steric
crowding).