Solid-phase synthesis of 5-arylhistidine-containing peptides: from linear antimicrobial peptides to cyclic peptides derived from arylomycins and aciculitins

The incorporation of unsymmetrical biaryl systems into peptide sequences is a strategy that can improve their biological activity. Due to the difficulty of arylating the 4(5}-position of the imidazole ring, this doctoral thesis was focused on the development of efficient methodologies for the solid-...

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Bibliographic Details
Author: Ng Choi, I-teng Montserrat
Format: doctoral thesis
Status:Published version
Publication Date:2015
Country:España
Institution:CBUC, CESCA
Repository:TDR. Tesis Doctorales en Red
OAI Identifier:oai:www.tdx.cat:10803/380739
Online Access:http://hdl.handle.net/10803/380739
Access Level:Open access
Keyword:Histidine
Histidina
Biaryl peptides
Pèptids biarílics
Péptidos biarílicos
Microwave irradiation
Irradiació de microones
Irradiación de microondas
Macroarylation
Macroarilació
Macroarilación
Arylomycins
Arilomicines
Arilomicinas
Suzuki-Miyaura reaction
Reacción Suzuki-Miyaura
Reacció Suzuki-Miyaura
547
Description
Summary:The incorporation of unsymmetrical biaryl systems into peptide sequences is a strategy that can improve their biological activity. Due to the difficulty of arylating the 4(5}-position of the imidazole ring, this doctoral thesis was focused on the development of efficient methodologies for the solid-phase synthesis of 5-arylhistidine-containing antimicrobial undecapeptides through a Suzuki-Miyaura reaction under microwave irradiation. The extension of this protocol allowed the preparation of biaryl cyclic peptides of different ring sizes bearing a His-Phe or His-Tyr biaryl linkage. Then, it was developed a procedure for the total solid-phase synthesis of biaryl cyclic lipopeptides derived from arylomycins. These strategies were extended to the preparation of biaryl cyclic analogues of the marine bicyclic pptides aciculitins. In particular, it was achieved the synthesis of analogues of the northern and the southern hemispheres of aciculitins as well as biaryl bicyclic peptides incorporating a Phe-Phe, a Phe-Tyr, a His-Tyr or a Tyr-Tyr biaryl bridge