SIKKIM UNIVERSITY

Department of Chemical Sciences

Strategies in Organic Synthesis: CHE-RS-E109
M.Phil, End Semester: December, 2017
Teacher: Dr. B. G. Roy

Full Marks: 50 Time: 2 hours

1. a) Rationalize the stereochemical outcome of the following process. 2

Stereoselectivity >97:3
b) Please predict the stereochemistry of the product and provide a mechanism that would support your
predictions. 3

c) Please provide correct mechanism for formation of following products. 5

i.

ii.

2. Give mechanism for following reactions. 2.5 x 4 =10

i.

ii.

iii.

iv.
3. a) Write suitable mechanisms for following transformations. 5

i.

ii.

b) What products do you expect from following multicomponent reactions? Give mechanisms for
their formations. 5

i.

ii.

4. a) Give mechanism for following transformation. 2

CH3
TsNHNH2, AcOH

O CH2Cl2, rt O
O

b) Give the step by step mechanism for following reaction sequence (reagents for each steps are given
below). 4

A: D-Glucose

i. a) PCC; b) Ph2=CH-CO2tBu; c) N- Iodosuccinimide, MeOH.

ii. a) HSn(n-Bu)3, AIBN; b) MeOH, H+

c) Give the step by step mechanism for following reaction sequence (reagents for each steps are given
below). 4

A: 2,3-O-isopropyliden-D-erithrofuranose.

i: a) BrPh3P(CH2)3CO2Et, KHMDS, THF; b) TsCl, Et3N; c) NaN3, DMF, heat.

ii: a) K2CO3, H2O, MeOH; b) Toluene, c) BH3.THF, H2O2, NaOH; d) HCl, THF
5. a) The C2-symmetric allylborane A introduced by Masamune has had an important impact on the
design of chiral aldol and allylation catalysts. Provide the absolute stereochemistry of the product of
this reaction. Provide a three dimensional drawing of the transition state for this reaction. 3

b) Fill the gaps in the following total synthesis. Give proper mechanisms their formation giving due
consideration to their stereochemistry. 7

6. a) French chemists were able to synthesize the hexasubstituted benzene 1 by the one-pot, five
component scheme shown below. This potentially diversity oriented synthesis proceeds through
intermediate A and B. Please propose an insightful mechanism accounting for 1, all byproducts
(Et3N+Cl-, NCBn, and 2H2O) and A and B. 5

b) In a study Aube has observed that the product of the following reaction is dependent on the tether
length between the azide and carbonyl functional groups. Provide mechanism for the transformations
in both cases and rationalize their difference in reactivity. 3

c) Provide a suitable mechanism for the following transformations 2

Thank you