Synthesis of phosphonic analogues of AAZTA†AAZTA=6-Amino-6-methylperhydro-1,4-diazepine-N,N′,N″,N″-tetraacetic acid.† and relaxometric evaluation of the corresponding Gd(III) complexes as potential MRI contrast agents

Guanci, Claudia; Pinalli, Roberta; Aime, Silvio; Gianolio, Eliana; Lattuada, Luciano; Giovenzana, Giovanni B.

doi:10.1016/j.tetlet.2015.02.118

Cited by 13 publications

(19 citation statements)

References 39 publications

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“…The mechanism likely occurs following the S N 1 pathway as reported above. This type of di- tert -butyl phosphonate was used for the synthesis of phosphonic acid analogues of peptides like protein-tyrosine kynases (PTKs) [ 134 ] or to prepare gadolinium complexes used as magnetic resonance imaging (MRI) contrast agents [ 135 – 136 ]. The introduction of the di- tert -butyl phosphonate was achieved by the reaction between di- tert -butyl phosphite and either benzyl halide [ 137 ] (Michaelis–Becker reaction) or aldehyde [ 134 ] (Pudovik reaction) or using tris- tert -butyl phosphite (Abramov reaction) [ 135 ].…”

Section: Reviewmentioning

confidence: 99%

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Phosphonic acid: preparation and applications

Sevrain¹,

Berchel²,

Couthon³

et al. 2017

Beilstein J. Org. Chem.

139

103

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The phosphonic acid functional group, which is characterized by a phosphorus atom bonded to three oxygen atoms (two hydroxy groups and one P=O double bond) and one carbon atom, is employed for many applications due to its structural analogy with the phosphate moiety or to its coordination or supramolecular properties. Phosphonic acids were used for their bioactive properties (drug, pro-drug), for bone targeting, for the design of supramolecular or hybrid materials, for the functionalization of surfaces, for analytical purposes, for medical imaging or as phosphoantigen. These applications are covering a large panel of research fields including chemistry, biology and physics thus making the synthesis of phosphonic acids a determinant question for numerous research projects. This review gives, first, an overview of the different fields of application of phosphonic acids that are illustrated with studies mainly selected over the last 20 years. Further, this review reports the different methods that can be used for the synthesis of phosphonic acids from dialkyl or diaryl phosphonate, from dichlorophosphine or dichlorophosphine oxide, from phosphonodiamide, or by oxidation of phosphinic acid. Direct methods that make use of phosphorous acid (H3PO3) and that produce a phosphonic acid functional group simultaneously to the formation of the P–C bond, are also surveyed. Among all these methods, the dealkylation of dialkyl phosphonates under either acidic conditions (HCl) or using the McKenna procedure (a two-step reaction that makes use of bromotrimethylsilane followed by methanolysis) constitute the best methods to prepare phosphonic acids.

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Section: Reviewmentioning

confidence: 99%

“…9 , the use of TFA induces the formation of the phosphonic acid 29 concomitantly with the formation of carboxylic acid from the tert -butyl ester. The final compounds were purified by removing the excess of TFA (72.4 °C at 1 bar) [ 138 ], using HPLC [ 137 ] or by precipitation in diethyl ether [ 136 ].…”

Section: Reviewmentioning

confidence: 99%

Phosphonic acid: preparation and applications

Sevrain¹,

Berchel²,

Couthon³

et al. 2017

Beilstein J. Org. Chem.

139

103

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“…Evaluation of such chelators as radiometal complexing agents would be relevant, especially with regard to the free carboxylate groups on the glutarate arms that could offer the possibility for conjugation reactions. To modulate more finely the number of coordinated water molecules in phosphorus AAZTA derivatives, Guanci et al synthesized mono-and diphosphonic analogues of AAZTA with a modified arm bore by the exocyclic amine, or one cyclic amine, or both amines of the diazepane ring [23]. Interestingly, the authors did not report the formation of the unwanted tricyclic bisaminal during the Mannich reaction involving AMPED, formaldehyde, and tritert-butyl phosphite (Scheme 2).…”

Section: Design Synthesis and Kinetic Properties 21 Original Aazta De...mentioning

confidence: 99%

“…Interestingly, faster exchange dynamics were observed for the (RS) de-Scheme 2. Synthesis sequence of phosphorus-containing AAZTA derivatives described by Ermelindo et al [21] and Guanci et al [23]. Ms = methanesulfonate.…”

Section: Design Synthesis and Kinetic Properties 21 Original Aazta De...mentioning

confidence: 99%

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AAZTA-Derived Chelators for the Design of Innovative Radiopharmaceuticals with Theranostic Applications

et al. 2022

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With the development of 68Ga and 177Lu radiochemistry, theranostic approaches in modern nuclear medicine enabling patient-centered personalized medicine applications have been growing in the last decade. In conjunction with the search for new relevant molecular targets, the design of innovative chelating agents to easily form stable complexes with various radiometals for theranostic applications has gained evident momentum. Initially conceived for magnetic resonance imaging applications, the chelating agent AAZTA features a mesocyclic seven-membered diazepane ring, conferring some of the properties of both acyclic and macrocyclic chelating agents. Described in the early 2000s, AAZTA and its derivatives exhibited interesting properties once complexed with metals and radiometals, combining a fast kinetic of formation with a slow kinetic of dissociation. Importantly, the extremely short coordination reaction times allowed by AAZTA derivatives were particularly suitable for short half-life radioelements (i.e., 68Ga). In view of these particular characteristics, the scope of this review is to provide a survey on the design, synthesis, and applications in the nuclear medicine/radiopharmacy field of AAZTA-derived chelators.

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