Erasmus Mundus Al Idrisi II

A scholarship scheme for exchange and cooperation

between Europe and North Africa
http://www.al-idrisi.eu

With the support of the Erasmus Mundus programme of the European Union

STUDY and RESEARCH PLAN

for Doctorates
ACADEMIC YEAR 2016 /2017- FIELD OF STUDY: Chemistry

Name of student: SAIDI Meriem

Home institution: University Abdelmalek Essadi (Tetouan)

Country: Morocco

DETAILS OF THE PROPOSED STUDY AND RESEARCH PLAN

Host institution: University of Granada

Country: Spain

Name of the academic programme / research unit : Natural products and applied organic synthesis
Proposed duration: 10 months
To be filled in ONLY if applicable:
COURSES AT HOST INSTITUTION
Course unit title

COURSE EQUAVILENCE AT HOME INSTITUTION

Course
unit code
(if any)

Numbe
r of
ECTS
credits

Course unit title

Master of chemistry
*Organic synthesis
strategy
*Inorganic solid state
chemistry
*Technical analysis and
characterization
*Planning experiments and
methodology
*Process interfaces
*Heterochemistry in
organic synthesis and
applications
*Molecular inorganic
chemistry
*Electrochemistry, basic
concepts and applications
*Quantum chemistry and
modeling
*The chemistry of natural
products and
carbohydrates
*Spectroscopic analysis in
Organic Chemistry

Course
unit code
(if any)

Number of
ECTS
credits
(h)

M1

100

M2

90

M3

99

MO1

75

M4

91

M5

100

M6

92

M7

100

M8

90

MC1

90

MC2

90

MO2

75

S4

400

Erasmus Mundus Al Idrisi II

A scholarship scheme for exchange and cooperation
between Europe and North Africa
http://www.al-idrisi.eu

With the support of the Erasmus Mundus programme of the European Union

*Initiation of the
Bibliography
Chemical and security
risks in a laboratory
*Startup phase of the
investigation

Description of planned research activities:

Preparation of bicyclic synthons by electrophilic cyclization of polyenes and derivatives
Merosesquiterpenes are natural products of mixed biosynthetic origin (polyketideterpenoid), which contain a sesquiterpene unit attached to a phenol or quinone fragment. The most
important group of this family of compounds, due to the wide variety of structural types presented
and its important and potent biological activity, are those with a bicyclic terpene fragment
(drimane).
Examples of drimenylquinones are taurine (1), with antitumor activity and inhibitor of the
cholesterol biosynthesis (J. Nat. Prod. 2008, 71, 218), (+)-hyatellaquinone (2) active against HIV
(J. Org. Chem. 1999, 64, 9318), or the sfingosine kinase inhibitor (-)-F-12509 A (3) (Tetrahedron
Lett. 2007, 48, 4865). Another important group of compounds belonging to the family of
merosesquiterpenes possess a tetracyclic system, resulting from the union of the bicyclic aromatic
moiety fragment through the phenolic oxygen, as in the case of puupehenone (4) (J. Org. Chem.
1995, 60, 7290) and cyanopuupehenone (5) (J. Org. Chem. 1993, 58, 6565) and related
compounds, also with considerable biological activity, or through a carbon of the aromatic ring, as
in the case of akaol A (6) (J. Nat. Prod. 2003, 66, 686) or dasyscyphin B (7) (Tetrahedron 2006,
62, 1828).
OH

OR
O

OH

R1
R2

O
R3

OH

OH

HO

2 R: Me
3 R: H

H
4 R: H
5 R: CN

H
6 R1: OH, R2: H, R3: CH2OMe
7 R1: H, R2: CH2OMe, R3: OH

The carbon skeleton of these compounds has been prepared in most cases by reaction of a
nucleophilic aromatic synthon with an electrophilic bicyclic synthon. The latter are generally
prepared by degradation of labdane diterpenes. Thus, the Alvarez-Manzanedas group has prepared
puupehenone (4), and some derivatives, from (-)-sclareol (Org. Lett. 2005, 7, 1477). Although less
common, the skeleton of these meroesequiterpenes has also been created by reacting a bicyclic
nor-sesquiterpene synthon, prepared from (-)-carvone, with an aromatic aldehyde (Tetrahedron
Lett. 2001, 42, 2389). Sometimes the bicyclic synthon is prepared by electrophilic cyclization of
2

Erasmus Mundus Al Idrisi II

A scholarship scheme for exchange and cooperation
between Europe and North Africa
http://www.al-idrisi.eu

With the support of the Erasmus Mundus programme of the European Union

the appropriate polyene, usually synthesized from the corresponding acyclic terpenoid (J. Org.
Chem. 2009, 78, 9196).

Specific objectives
The preparation of polycyclic compounds by electrophilic cyclization of polyenes is
advantageous in some cases, due to the easy availability of the polyene compounds and the
possibility of introducing a functionality in the A ring of the bicyclic system, depending on the
electrophile to be used for cyclization. The development of enantioselective processes also enables
to access to enantiomerically pure derivatives. It will be investigated electrophilic cyclization
proccesses of (E) -2,6,10-trimetilundeca-1,5,9-triene (8) and its 9-epoxy derivative 9 to obtain
bicyclic synthons functionalized in the A ring A, as 10 and 11, suitable for the preparation of
merosesquiterpenes of interest.
E+
E

10
Acid
HO

O
9

H
11

Compounds 8 and 9 will be synthesized starting from commercial geranylacetone (12),

following the sequences below depicted.

HO

12

OH

1) NBS
O

pTsOH
13

2) K2CO3

14
CeCl3
NaI

Ph3P=CH2

Ph3P=CH2
O
8

O
9

15

The cyclization of polyene 8 will be conducted utilizing various electrophiles, acids (Helv.
Chim. Acta 2006, 89, 3071), halogenated reagents (J. Am. Chem. Soc. 2010, 132, 14303) or sulfur
derivatives (Tetrahedron Lett. 1989, 30, 1499). Cyclization processes of the epoxy derivative 9 will
3

Erasmus Mundus Al Idrisi II

A scholarship scheme for exchange and cooperation
between Europe and North Africa
http://www.al-idrisi.eu

With the support of the Erasmus Mundus programme of the European Union

be carried out using different Bronsted and Lewis acids (J. Org. Chem.1994, 59, 2324).

Students signature: SAIDI

Meriem

Place and date: TETOUAN (MOROCCO) 04/01/2016

SENDING INSTITUTION
We confirm that the proposed study and research plan is approved.
Coordinator at Faculty/Department Level:

Contact Person for Erasmus Mundus Al Idrisi:

Signature and stamp:

Signature and stamp:

Date:

Date:

RECEIVING INSTITUTION
We confirm that the proposed research plan is approved.
Coordinator at Faculty/Department Level:

Contact Person for Erasmus Mundus Al Idrisi:

Signature and stamp:

Signature and stamp:

Date:

Date: