IFCPAR AR (ENGLISH) for CD - CEFIPRA

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Pure & Applied Chemistry
Dr. G. V. M. Sharma
Organic Chemistry Division III
Indian Institute of Chemical Technology
Hyderabad
Prof. Christian Bruneau
UMR 6226 CNRS
Université de Rennes I
Rennes
Project 3805-2
NON-NATURAL PEPTIDES IN ASYMMETRIC
CATALYSIS: METAL-MEDIATED SYNTHESIS OF PEPTIDE-BASED
MATERIALS AND THEIR APPLICATIONS
IFCPAR
Indo-French Centre for the Promotion of Advanced Research
Duration: Three years (September, 2008 to August, 2011)
Objectives
The project aim was to synthesize new catalysts and use them to
develop a variety of functionally diversified amino
acids/peptides and new materials for asymmetric catalysis and
for biomedical applications. The project was expected to lead
to not only novel catalysts, non-natural amino acids, peptides
but also nanoparticles biomaterials organic-inorganic hybrids,
and the peptide-metal enantioselective catalysts.
Accomplishments
i) Preparation of various peptide substrates with unsaturated
side chains was achieved. The RCM mediated cyclization of
different peptides resulted in interesting results. The systems
which would result in 11 and 13-membered rings,
underwent facile cyclization, while, the systems that are
expected to give 9-membered rings were found to be
reluctant to RCM. Likewise, yet another interesting
observation on the RCM of a different dipeptide was in the
formation of a selective head-to-tail double cross
metathesis product from two units
ii) The studies helped in deriving the factors that are governing
the cyclisation and macrocyclization reactions. The results
on the formation of unexpected products during RCM
helped in designing newer systems for further studies to
prove the found observations
iii) Six-membered ring ruthenium complexes featuring
phosphino sulfonate moieties as β-amino
acid surrogates
were also prepared. Evaluation of these complexes led to
the development of sustainable transformations such as
allylation of indole derivatives with allylic alcohols with the
generation of water as sole by product. More recently, first
ruthenium-catalyzed C(3) functionalization of cyclic amines
with aldehydes has been developed. Two new ruthenium 6membered
ring complexes based on the Ru(p-cymene)
core and -amino acid ligands have been prepared.
Application of these complexes would lead to the
development of enantioselective versions of the recent
application. Other hydrogen transfer reactions will not be
discarded considering the potential of such methodology
Research papers published: Five