Porphyrins, macrocyclic

The preparations of chlorins described so far by attack of different reagents at a peripheral C — C double bond of the porphyrin macrocycle are all restricted to highly symmetric porphyrins because otherwise complex mixtures of constitutional isomers can be formed. The problem of... 

The concept of expansion of the porphyrin macrocycle by formally inserting additional carbon atoms between the pyrrole rings was first considered and synthetically realized by LeGoff/ He also suggested a nomenclature for these macrocyclic systems using the word platyrin which... 

Electronic effects on the reactions of [Rh(Por)h dimers and hydrides were probed by varying the porphyrin macrocycle. OEP and TPP vary considerably in their properties, with OEP being one of the strongest and TPP one of the weakest (7-donors among porphyrin derivatives. However. Rh(Por)]2, Rh(Por)H, and Rh(Por)r showed the same reactivity in a variety of reactions for both OEP and TPP, indicating that electronic effects relating to the porphyrin ligand have... 

The prevalence of the heme in O2 metabolism and the discovery in the 1960s that metallophthalocyanines adsorbed on graphite catalyze four-electron reduction of O2 have prompted intense interest in metaUoporphyrins as molecular electrocatalysts for the ORR. The technological motivation behind this work is the desire for a Pt-ffee cathodic catalyst for low temperature fuel cells. To date, three types of metaUoporphyrins have attracted most attention (i) simple porphyrins that are accessible within one or two steps and are typically available commercially (ii) cofacial porphyrins in which two porphyrin macrocycles are confined in an approximately stacked (face-to-face) geometry and (iii) biomimetic catalysts, which are highly elaborate porphyrins designed to reproduce the stereoelectronic properties of the 02-reducing site of cytochrome oxidase. 

Based on studies showing that the close proximity between the porphyrin and the Cm is essential for the observation of an electron transfer process, Fukuzumi and co-workers have prepared the porphyrin-C6o diad 41, in which the C6o-pyrrolidinyl moiety is directly connected to the meso position of the porphyrin macrocycle (Scheme 12) <03JPC(A)8834>. The strategy adopted for the synthesis of the starting porphyrin involved the 2+2 condensation of a maso-unsubstituted dipyrrylmethane with 3,5-di-tert-butylphenyl-substituted dipyrrylmethane and 3,5-di-tert-butylbenzaldehyde, to give 39, in 11.5% yield. Subsequent Ni(II) metallation, followed by Vilsmeier-Haack formylation and demetallation, gave rise to 40 which was used as the 1,3-dipole precursor this dipole in the presence of N-methylglycine and C6o, yielded the expected diad 41. 

Similar protocols have been followed for the synthesis of other porphyrin-C6o diads where the linkage between Cm and porphyrin moieties occurs through the ortho, meta or para positions of the phenyl ring of the porphyrin macrocycle <00PP598, 03JPC(A)8834 and 06SC2135>. 

Besides the use of porphyrins as azomethinic ylide derivatives, the porphyrin macrocycle can also be used to generate porphyrinic nitrile oxides 55 (Scheme 17) <04RCB(E)2192>. Thus, the treatment of oxime 54 with /V-bromosuccinimide in the presence of triethylamine, led to the formation of nitrile oxide 55, which was trapped in 1,3-DC reactions with dimethyl maleate and 2,5-norbomadiene to afford 56 and 57, respectively. In the reaction with 2,5-norbomadiene, if an excess of 55 was used, then the corresponding bis-adduct was obtained in good yield. 

Finally, it is important to mention that there are other related publications in which porphyrin macrocycles are not directly used as dipolarophiles but are transformed into new derivatives that can react with carbonyl ylides via ACE (alkene cyclobutene epoxide) reactions. This idea arose in 1997, when Russell and co-workers found that fused ester-activated cyclobutene epoxides 86 can be ring-opened to give carbonyl ylides 87, and that these can be trapped stereospecifically by ring-strained alicyclic dipolarophiles, such as 2,5-norbomadiene, to form hetero-bridged norbomanes 88 in good yields, through ACE transformations (Scheme 31) <97CC1023>. 

This survey has highlighted the importance of cycloaddition reactions as powerful tools for the functionalisation of meso and beta-positions of a porphyrin macrocycle. 

It needs to be noted that when the ligand system contains extensive unsaturation, then oxidation of the corresponding complex may yield a product containing a stabilized cation radical (rather than one in which the metal oxidation state has been altered). For example, such a situation has a tendency to occur on oxidation of divalent metal complexes [including Ni(n)] of the tetraphenyl-substituted porphyrin macrocycle. 

On coordination, the porphyrin macrocycle loses two protons (to yield a neutral complex when the central metal ion is divalent). The extensive electron delocalization throughout the ligand will normally extend to the central metal when the latter is covalently bound to the porphyrin. As expected, such complexes are extremely stable this is undoubtedly important to the biological role of these complexes. 

The synthesis of metalloporphyrins which contain a metal-carbon a-bond can be accomplished by a number of different methods(l,2). One common synthetic method involves reaction of a Grignardreagent or alkyl(aryl) lithium with (P)MX or (PMX)2 where P is the dianion of a porphyrin macrocycle and X is a halide or pseudohalide. Another common synthetic technique involves reaction of a chemically or electrochemically generated low valent metalloporphyrin with an alkyl or aryl halide. This latter technique is similar to methods described in this paper for electrosynthesis of cobalt and rhodium a-bonded complexes. However, the prevailing mechanisms and the chemical reactions... 

The use of porphyrinic ligands in polymeric systems allows their unique physio-chemical features to be integrated into two (2D)- or three-dimensional (3D) structures. As such, porphyrin or pc macrocycles have been extensively used to prepare polymers, usually via a radical polymerization reaction (85,86) and more recently via iterative Diels-Alder reactions (87-89). The resulting polymers have interesting materials and biological applications. For example, certain pc-based polymers have higher intrinsic conductivities and better catalytic activity than their parent monomers (90-92). The first example of a /jz-based polymer was reported in 1999 by Montalban et al. (36). These polymers were prepared by a ROMP of a norbor-nadiene substituted pz (Scheme 7, 34). This pz was the first example of polymerization of a porphyrinic macrocycle by a ROMP reaction, and it represents a new general route for the synthesis of polymeric porphyrinic-type macrocycles. 

Cationic porphyrinic macrocycles, in particular the archetypical tetracationic, meso-telra-W-melhylpyridyl (porphyrin, have applications in biology, medicine, catalysis, and materials (95-103). Cationic tetraazaporphyrins, or porphyrazines, which represent a novel alternative and class of cationic porphyrinic compounds, were recently reported (37). 

In order to prepare asymmetric meso-porphyrinylsugar derivatives (mono-, di- and tri-glycosylarylporphyrins), pyrrole was condensed with a mixture of glycosylated and nonglycosylated aldehydes.17,21,24,44 46 Several porphyrinylsugar derivatives were prepared by this synthetic methodology. The saccharide unit can be directly linked to the porphyrin macrocycle 35-50 or separated from the phenyl group by a spacer, such as in the case of derivative 51-53 shown below (Fig. 4). 

However, in contrast to the human His25Ala HO-l heme complex, which has no detectable activity in the absence of imidazole (78), the His20Ala Hmu O rheme complex in the presence of NAD PH and NADPH-cytochrome P450 reductase was foimd to catalyze the initial meso-hydroxylation of the heme (151). The product of the reaction was Fe verdoheme, as judged by the electronic absorption spectrum and the detection of carbon monoxide as a product of the reaction. Hydrolytic conversion of the verdoheme product to biliverdin and subsequent HPLC analysis confirmed that the oxidative cleavage of the porphyrin macrocycle was specific for the a-meso-carbon. 

Cytochromes serve as electron donors and electron acceptors in biological electron transfer chains, and with >75,000 members (53) they provide the bulk of natural heme proteins in biology. Cytochromes may be fixed into place within an extended electron transfer chain, such as the membrane-bound 6l and 6h of the cytochrome bci complex, or may be soluble and act as mobile electron carriers between proteins, for example, cytochrome c (54). In either role, the cytochrome may be classified by the peripheral architecture of the porphyrin macrocycle. Figure 1 shows the dominant heme types in biological systems, which are hemes a, b, c, and d, with cytochomes b and c being most prevalent. The self-association of a protein with heme via two axial ligands is a... 

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