Q.

Compound A reacts faster by the SN2 mechanism than the compound B

Q. Compound A reacts faster by the SN1 mechanism than compound B

Reactive differences between axial and equatorial conformers

Nu-

TS

Nu-

Nu- = -SPh
X- = -OTs TS
Reaction 1 found to be 31 times faster than 2

hindered by axial
hydrogens
Which of the following compound will be faster reacting
under the given reaction condition?
Epoxide formation

No epoxide

Only diaxial conformation forms epoxide

E2 eliminations have anti-periplanar transition states

Two conformations with H and X coplanar

In E2 eliminations, the new π bond is formed by overlap of the

C-H σ bond with the C-X σ* antibonding orbital
 E2 Stereochemistry

E2 reactions occur most rapidly when the H-C bond and C-LG bonds involved are
co-planar, most often at 180o with respect to each other. This is described as
an antiperiplanar conformation. This conformation positions the σ bonds that are
being broken in the correct alignment to become the π bond.

The staggered, antiperiplanar alignment is preferred

because it aligns the two σ bonds that become the π bond.
 Synperiplanar arrangments where the angle between the H-C bond
and C-LG is 0o are also known, usually in systems that are either inflexible
rings or intramolecular eliminations.

The eclipsed, synperiplanar alignment also aligns the two

σ bonds that become the π bond, but is less favourable than
the antiperiplanar arrangement.

These alignments are example of a stereoelectronic effect because they involve the
specific spatial positioning of the bonds (electrons) in order for the process to occur

We will discuss “Syn” elimination at a later stage

E2 eliminations have anti-periplanar transition states

Me groups gauche Me groups

(syn-clinal) anti-periplanar
more hindered Less hindered

Reaction is stereoselective
Only one proton for removal
Whereas
 Relative reactivity of alkyl halides in E2 elimination
Relative reactivity of alkyl halides in E2 reaction
Tertiary alkyl halides > secondary alkyl halides > primary alkyl halides

Stability of the generated alkene is the decisive factor

Q1. Which alkyl halide in each pair is more reactive in an E2 reaction with NaOH
Q2. Which alkyl halide in each pair is more reactive in an E2 reaction with NaOH
Q.

Slow
Anti 1,2-elimination and conformational requirements
Q1. Among the two given compounds (A & B) one undergoes E2 reaction
swiftly with NaOMe/MeOH than the other. Identify A and B with proper
reason

Q2. Explain the following reaction with proper explanation

Q.

S N2
Reactions of 2-bromo-4-phenylcyclohexanols with base and silver oxide

Ag2O
or OH- Ag2O Ag2O
or OH- Or OH-

Stable not suitable for -HBr

Ag2O
Ag2O induces –Br -

OH-
Esterification and hydrolysis reaction of conformationally locked cyclohexane systems
Esterification and hydrolysis reaction of conformationally locked cyclohexane systems
Which of the following isomer will be tosylated first with 1 eq
of Ts-Cl and pyridine? Explain your answer with proper reasoning.
Also predict the proper stereochemistry of the final product?
Arrange the following alcohols in order of decreasing rate
of esterification with para-nitrobenzoyl chloride?
Esterification and hydrolysis reaction of conformationally locked cyclohexane systems
Which compound should saponify faster (A or B)?
Explain the relative rate differences?
Which of the “OH” group in the following compound will oxidize
rapidly in presence of PCC. Explain your answer with proper reasoning?

The secondary axial alcohol will be oxidized first.