Κατεύθυνση Οργανική Σύνθεση και Εφαρμογές της στη Χημική Βιομηχανία
Library of the School of Science

2014-01-15

2014

Βορεάκος Κωνσταντίνος

Δημήτριος Γεωργιάδης Επίκ. Καθηγητής ΕΚΠΑ, Αθανάσιος Γκιμήσης Αναπλ. Καθηγητής ΕΚΠΑ, Βικτωρία Μαγκριώτη Λέκτορας ΕΚΠΑ

Διερεύνηση μεθοδολογίας για τη σύνθεση φωσφινοπεπτιδικών δομών περιορισμένης διαμορφωτικής ελευθερίας, αναλόγων των δ-λακταμών

Greek

Methodology study on the synthesis of conformationally constrained phosphinic peptide compounds, δ-Lactams analogues

In the present thesis our main goal was the synthesis of conformationally
constrained phosphinic compounds which has been achieved by introducing a
bridge connecting P1 and P1΄ positions of the peptide backbone. Introduction of
structural elements that cause rigidity in bioactive phosphinic pseudopeptides
can stabilize specific conformations of the compounds which fit ideally within
the active center of the enzyme.
The synthesis phosphinic pseudopeptide analogues of δ-lactams, can be achieved
starting from very simple substrates. These compounds can be synthesized by
cyclization of dienes using a ring closing metathesis reaction.
An essential point in the successful attempt to synthesize phosphinic
derivatives of δ-lactams is the formation of the P-C bond which connects the P1
and P1΄ parts of the peptide backbone.
The reaction of allylic substitution of suitable electrophiles from silyl
phosphonites, which are synthesized in situ from intermediate, was chosen to
perform this critical step. The electrophiles can be easily synthesized from
Baylis-Hillman derivatives. An advantage of this methodology is that allylic
substitution leads to the formation of a conjugated bond in the position P1΄
which is susceptible to reactions of conjugate addition.

δ-Lactams, Conformationally constrained phosphinic compounds, Baylis-Hillman, Ring Closing Metathesis, Αllylic substitution

Yes

ΧΙΙΙ-XV, XVII, ΧΙΧ

Yes

129

XXII, 130

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https://pergamos.lib.uoa.gr/uoa/dl/object/1316841