Moon Javed

223683357
Project Assignment
Chem 541
Structure: 163
Submitted To:
Dr. Seemal Jelani
Name of reagents:
1. Methyl vinyl ketone (MVK)
2. iodomethane (MeI)
3. Potassium tert-butoxide (BuOK)
4. Acetic acid (AcOH)
5. Zinc (Zn)

One of the steps involved in Total synthesis of Limonin:

In my reaction (3aR,5aS,6R,9aS,9bS)-6-chloro-6-ethyl-3a,9a-dimethyl-3-methylenedecahydro-1H-
cyclopenta[a]naphthalen-7(2H)-one compound with dioxygen (1:1) (162) was converted
into (8S,9S,10S,13R,14S)-ethyl 4,4,8,13-tetramethyl-17-methylene-3-oxo-
2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthrene-10-carboxylate i.e. (163)
in the literature.

Reaction Steps:
This reaction consists of three steps:
1. Reductive dichlorination
In this step addition of hydrogen is done and chlorine atoms is removed that's why this step is known as
reductive dichlorination.

2. Robinson Annulation
It will give rise to a six membered ring by forming three new carbon-carbon bonds.
Annulation word means building a ring. It was introduced in 1935 by Robert Robinson.
Specifically the synthesis of cortisine is completed through the use of the Robinson annulation. Synthesis of
cortisone is completed through the use of robinson annulation.
It is also used in the synthesis of antibiotic and steroids.
Robinson annulation is an organic chemical reaction used to construct a six-membered ring structure. This
method uses a ketone and an α, β-unsaturated ketone to form a bicyclic system containing a substituted
cyclohexenone system in a sequential combination of Michael addition and intramolecular aldol
condensation.  The word ‘annulation’ means ‘building a ring.

3. Gamma Deprotonation
3rd step we go for gamma deprotonation means the hydrogen ions are removed from gamma carbons. Along
with methylation sequence will be done so to double bond structure will be formed. So after passing through
these three steps so we come with a structure of 163.

Name of Product:
(8S,9S,10S,13R,14S)-ethyl 4,4,8,13-tetramethyl-17-methylene-3-oxo-2,3,4,7,8,9,10,11,12,13,14,15,16,17-
tetradecahydro-1H-cyclopenta[a]phenanthrene-10-carboxylate