Refernces
10.1016/j.tet.2005.03.086
The research focuses on the synthesis and variation of m-THPC (Temoporfin) related amphiphilic A2BC-type porphyrins for applications in photodynamic therapy (PDT). The study explores the role of photosensitizer localization and aims to develop new photosensitizers by synthesizing unsymmetrically substituted tetrapyrroles with mixed hydrophilic/hydrophobic substitution patterns. The experiments involve the use of well-established condensation methods combined with functionalization via organolithium compounds or transition metal-catalyzed coupling protocols. Starting from simple A2- or AB-porphyrins, the researchers describe the synthesis of various A2B-, A3-, A3B-, and A2BC-porphyrins. The reactants include dipyrromethane, aldehydes, and organolithium reagents, while analyses are performed using techniques such as NMR, UV/vis spectroscopy, mass spectrometry, and elemental analysis to characterize the synthesized porphyrins and evaluate their potential as photosensitizers in PDT.
10.1021/ic0011112
The research investigates the activation of aromatic and benzylic C-H bonds in the system involving bis(dicarbonylrhodium(I))porphyrinate-hydrocarbon solvent. The study aims to understand the reactivity of Rhodium (Rh) complexes with different oxidation states (RhI, RhII, and RhIII) towards C-H bonds, particularly focusing on the differences in reactivity between monometallic and bimetallic Rh complexes. The researchers used various porphyrin complexes, including Rh2(CO)4(por) (where por represents different porphyrin dianions such as OEP or TPP), RhIII(OEP)(PF6), and RhIII(TPP)(O2), along with hydrocarbon solvents like benzene, toluene, and anisole. The conclusions drawn from the study suggest that the activation of aromatic and benzylic C-H bonds in Rh2(CO)4(por) systems at elevated temperatures is attributed to RhII(por) and RhIII(por) derivatives, rather than the intrinsic reactivity of Rh2(CO)4(por) itself. The research provides insights into the potential for designing better catalysts and offers a synthetic route to organometallic RhIII(por) species, which are relevant to the reactivity of cobalamine in vitamin B12.
10.1021/jo00086a035
This research presents the synthesis, characterization, and spectroscopic properties of a novel class of meso-C-glycoconjugated porphyrins, specifically 5,15-di-C-glycosyl-10,20-diarylporphyrins. The purpose of the study was to create porphyrin-sugar carbon conjugates, which have potential applications in mimicking the properties of heme-containing enzymes and constructing molecular recognition devices. The researchers achieved this by condensing suitable dipyrrylglycosides with aryl aldehydes in the presence of trifluoroacetic acid or BF3 promoters, yielding porphyrins 9-14. The study concluded that these porphyrins exhibit inherently distorted macrocycles, as indicated by red-shifted UV-vis spectra, and adopt distorted saddle conformations in solution, as confirmed by 1D and 2D 1H NMR spectroscopic studies and molecular mechanics analysis. The chemicals used in the process include various dipyrrylglycosides, aryl aldehydes, trifluoroacetic acid, BF3, and DDQ, among others.
10.1142/S1088424610002367
The research investigates the synthesis, photophysical properties, and electronic interactions of a series of oxacalix[4]arene-linked cofacial bisporphyrins (compounds 2–4). The study aims to explore the effects of different metal ions (zinc and copper) on the electronic interactions between the two porphyrin macrocycles in these bisporphyrins. Porphyrin is a macrocyclic compound known for its rich photophysical and electrochemical properties. In this study, porphyrins are used as the core chromophores in the bisporphyrin structures. The researchers used UV-vis, fluorescence, and cyclic voltammetry studies to analyze the properties of these compounds. They found that the free-base bisporphyrin 2 and biszinc(II)porphyrin 3 exhibited little electronic interaction between the porphyrin macrocycles, while the biscopper(II)porphyrin 4 showed enhanced electronic communication due to the closer proximity of the porphyrin macrocycles (7.108 ?) compared to 2 (8.471 ?) and 3 (8.557 ?), as determined by HF/CEP-31G computational methods. The study concludes that the insertion of copper(II) ions significantly influences the electronic and photophysical properties of the bisporphyrins, suggesting potential applications in light-harvesting and electron transfer materials.
10.1021/ja00245a068
The research focuses on two main chemical investigations. The first part of the research delves into the synthesis of new tmtaa-metal derivatives using the reactive species Li2tmtaa, an approach that contrasts with the traditional use of tmtaaH2 and yields promising results. The study emphasizes the structural characterization of metalloporphyrin dimers and their electronic properties, with molybdenum atoms and porphyrin moieties playing a central role in the described compounds. The second part of the research introduces a novel route to Allenyl Fluorides, specifically the synthesis of 4-Amino-7-fluorohepta-5,6-dienoic Acid, which is the first fluoroallenyl amino acid. This synthesis is significant as it provides a practical route to fluoroallenes, a functional group with potential applications in enzyme-activated irreversible inhibitors and other biologically active species. The chemicals used in the process include n-BuLi, Mo2(OAc)3, Na-Hg, ferricinium salts, and various solvents and reagents for the synthesis, extraction, and characterization of the target compounds. The conclusions drawn from the research highlight the successful synthesis of the desired fluoroallenes and the potential for further exploration in fluoroallenes chemistry and enzymology.