UNIVERSITY OF GUYANA

FACULTY OF NATURAL SCIENCES

DEPARTMENT OF CHEMISTRY
CHM 3107 – ORGANIC CHEMISTRY II

ASSIGNMENT 1
Due Date: 19th January, 2022
Name: Trimal Accra
USI: 1032430
1. Strychnine, has the structure shown in Figure 1.

Figure 1: Structure of Strychnine

(a) State whether strychnine is an acid, neutral or a base. [1 mark]

Strychnine is a basic compound.

Discuss the resolution of a racemic compound that is an acid. [6 marks]

Because the intermediates created lack regioselectivity, when chiral products

are synthesized from achiral reagents, the resultant mixture is frequently a

mixture of the two enantiomeric forms. These mixtures, also known as

racemates or racemic mixtures, are 50:50 enantiomer mixtures. Physical

properties of these enantiomers differ just slightly, making separation

challenging. A racemic acid can be resolved by reacting it with the one

enantiomeric form of a chiral base to produce a mixture of diastereomers.

When a (S) base reacts with a racemic mixture of the acid's (S) and (R)

enantiomers, (R-S) and (S-S) diastereomers are produced. Unlike enantiomers,

these diastereomers have different physical properties and can be physically

separated using procedures such as crystallization. The diastereomer mixture

is crystallized in this process, and the two diastereomers crystallize

 separately, resulting in crystals of distinct shape/size that can be

distinguished. The base can then be removed from the separated

diastereomers by treating them with an acid that is stronger than the chiral

acid, isolating the chiral acid's (S) and (R) enantiomers. Strychnine, the

chemical seen above, is a common chiral base used to resolve racemic

combinations of chiral acids. The base used is determined by the relative ease

with which the diastereomers generated can be separated (physical properties

of disatereomers differ) and the ease with which the base can be recovered

from the acid. The separation of (R)-lactic acid and (S)-lactic acid by reaction

with (S)-1-phenylethylamine is an example of this resolution (Siedlecka, 2013).

2. (a) List two essential conditions for chirality in biphenyls. [2 marks]

 Bulky groups must be present on the orthro locations of the aromatic rings to

prevent the two benzene rings from co-planarily rotating around the connecting

bond due to repulsion.

 When looking down the chirality axis, the two adjacent groups must be distinct

because comparable groups would form a plane of symmetry, rendering the

molecule achiral. For the same reason, the two remote groups must be distinct

from one another.

 2013 (Katritzky).

(b) What is meant by the term atropisomers? [5 marks]

 Atropisomers are stereoisomers that develop as a result of impeded rotation

around a single bond, when energy differences caused by steric strain or

other factors provide a high enough barrier to rotation to allow distinct

conformers to be isolated. It's like though someone is intruding into your

personal area. Isn't it normal for you to back away when something happens?

With steric tension, it's the same thing. To avoid any repulsive interactions,

the atoms try to maximize distance between them. Single bonds should be

able to spin freely, but in atropisomers, the steric strain is so great that the

molecules become stuck or trapped in one specific conformation and cannot

rotate.

3. (a) Assign R/S descriptors to compound (A) shown in Figure 2. [3 marks]

Figure 2: structure of compound (A)

(b) Write the stereochemical name of compound (A). [1 mark]

4. Consider the structure shown in Figure 3.

(a) Identify using asterisk the stereocenters

present in the structure. [1 mark]

Figure 3: Structure of camphor

(b) How many possible stereoisomers could this molecule have? Explain. [4 marks]

There are 2n stereoisomers for a molecule with n stereogenic centers.

Because n=2 in this situation, 22=4 stereoisomers should exist, however this

is not the case. Because the two stereogenic centers are connected, camphor

only possesses two stereoisomers. Due to the bicyclic linkage, the entire

molecule would have to flip on itself in order for one stereocentre to invert and

form a distinct stereoisomer, a phenomena with an extremely high energy

barrier. As a result, the only stereoisomers that exist are the borneol and

isoborneol mirror images (enantiomers). Because the doubly linked oxygen is

closer to one stereogenic centre than the other, any conceivable symmetry

planes are eliminated, we can ensure that the mirror images are isomers

(Nasipuri, 2005).

(c) Explain why for camphor the number of stereoisomers is generally lesser than its

acyclic counterpart. [3 marks]

 This is because camphor is bicyclic, with a bridge carbon connecting the two

stereogenic centers. Because the entire molecule would have to twist in on

itself to generate stereoisomers, the two stereogenic centres cannot invert to

form stereoisomers. This is a very high energy position that is not really

conceivable. As a result, only two stereoisomers, the two mirror versions of

camphor, exist. The stereogenic centre substituents would be able to twist

without too much strain if the bridge carbon was absent, resulting in the

creation of all four stereoisomers (Nasipuri, 2005).

5. (a) Define dynamic stereochemistry. [2 marks]

Dynamic stereochemistry is a branch of chemistry that explores the impact of

stereochemistry on the pace of a chemical process. Stereochemistry is used in the

following applications:

 Stereotypical responses

 Asymmetric or stereoselective reactions

 Racemisation processes

(b) With reference to dynamic stereochemistry, list the types of substrates that are

considered in the study of conformation and reactivity.

1. Conformationally rigid diastereomers: These are stereoisomers where groups of interest

are rigidly locked in place. An example is trans-2α-decalol and trans-2β-decalol where the

hydroxyl group is locked into the equatorial and axial positions respectively. These

conformers cannot interconvert. There exists a direct relationship between conformer and

reactivity.
 2. Conformationally mobile diastereomers: Stereoisomers with groups that can change

position such as disubstituted cyclohexanes which can interconvert axial and equatorial

positions through ring flipping. The relative specific reaction rates of two conformationally

mobile diastereomers depends on the rates of each constituent conformer and their

populations in the equilibrium mixture of each diastereomer.

3. Substituents with two or more conformers: The overall reaction rate (k) of a substrate

with multiple conformers depends on the specific reaction rates of each conformer and

their initial populations in the reaction mixture (in mol fraction). It is given by the

equation: k = ∑niki.

Where k is the overall reaction rate; ni is the mol fraction of the ith conformer; ki is the

specific reaction rate of the ith conformer.

(Wolf, 2008).

(d) State the name of the quantitative treatments available for correlating conformation

and reactivity in systems in which conformational interconversion is faster than the

reaction rates. [2 marks]

 Winstein-Eliel rate equations

 Curtin Hammett Principle

Reference:

Katritzky, A. R. (2013). Handbook of Heterocyclic Chemistry. Burlington: Elsevier Science.

Nasipuri, D. (2005). Steroisomerism: Axial chirality, Planar chirality and Helicity. In Stereochemistry of
organic compounds (pp. 72-105). New Delhi: New age international (p).

Siedlecka, R. (2013). Recent developments in optical resolution. Tetrahedron, 69(31), 6331-6363.

doi:10.1016/j.tet.2013.05.035

Wolf, C. (2008). Dynamic stereochemistry of chiral compounds principles and applications. Cambridge,
UK: RSC Publishing.