Synthèse de méso-α,γ bis(diamino-2,6 phényl) porphyrines

Lecas-Nawrocka, Alexandra; Levisalles, J.; Mariacher, Claire; Renko, Zafiarisoa; Rose, Éric

doi:10.1139/v84-351

Cited by 17 publications

(3 citation statements)

References 8 publications

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“…Route A is based on the acid-catalyzed condensation of meso -unsubstituted dipyrromethanes with aromatic aldehydes. , This route has been used in the past for preparation of various types of 5,15-diaryloctaalkylporphyrins. ,, The alternative route has two major variants: B , the classical MacDonaldʼs method, in which the substituent-free methine groups in the target porphyrin originate from the formyl groups in 1,9-diformyldipyrromethanes, and B′ , the method of Baldwin et al, which makes use of the condensation of 1,9-unsubstituted 5-aryldipyrromethanes with orthoformate. A variant of the latter reaction, employing N , O -acetal of formaldehyde (EtOCH 2 NBn 2 ), has been used to synthesize Ar 2 TCHPs, but the practical value of this method was undermined by a significant degree of scrambling.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of 5,15-Diaryltetrabenzoporphyrins

et al. 2008

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A general method of synthesis of 5,15-diaryltetrabenzoporphyrins (Ar 2 TBPs) has been developed, based on 2 + 2 condensation of dipyrromethanes followed by oxidative aromatization. Two pathways to Ar 2 TBPs were investigated: the tetrahydroisoindole pathway and the dihydroisoindole pathway. In the tetrahydroisoindole pathway, precursor 5,15-diaryltetracyclohexenoporphyrins (5,15-Ar 2 TCHPs) were assembled from cyclohexeno-fused meso-unsubstituted dipyrromethanes and aromatic aldehydes or, alternatively, by way of the classical MacDonald synthesis. In the first case, scrambling was observed. Aromatization by tetracyclone was more effective than aromatization by DDQ but failed in the cases of porphyrins with electron-withdrawing substituents in the meso-aryl rings. The dihydroisoindole pathway was found to be much superior to the tetrahydroisoindole pathway, and it was developed into a general preparative method, consisting of (1) the synthesis of 4,7-dihydroisoindole and its transformation into meso-unsubstituted dipyrromethanes, (2) the synthesis of 5,15-diaryloctahydrotetrabenzoporphyrins (5,15-Ar 2 OHTBPs), and (3) their subsequent aromatization by DDQ. Ar 2 TBP free bases exhibit optical absorption spectra similar to those of meso-unsubstituted tetrabenzoporphyrins and fluoresce with high quantum yields. Pd complex of Ph 2 TBP was found to be highly phosphorescent at room temperature.

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Section: Resultsmentioning

confidence: 99%

Synthesis of 5,15-Diaryltetrabenzoporphyrins

et al. 2008

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“…The resulting precipitate was collected by suction filtration and recrystallized from 95% ethanol to yield the benzyl ester (10.54 g, 37.0 mmol, 82%) as white crystals, mp 73–75 °C (lit. mp 75–76 °C); 1 H NMR (500 MHz, CDCl 3 ) δ 0.91 (3H, t, J = 7.2 Hz), 1.28–1.43 (4H, m), 2.18 (3H, s), 2.28 (3H, s), 2.35 (2H, t, J = 7.5 Hz), 5.29 (2H, s), 7.30–7.34 (1H, m), 7.35–7.39 (2H, m), 7.41–7.43 (2H, m), 8.56 (1H, s, br); 13 C NMR (CDCl 3 ) δ 10.9, 11.8, 14.2, 22.7, 23.9, 33.3, 65.5, 116.5, 122.8, 128.2, 128.3, 128.7, 130.0, 136.9, 161.4. Anal.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of Indenoporphyrins, Highly Modified Porphyrins with Reduced Diatropic Characteristics

et al. 2011

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Indene-fused porphyrins have been synthesized starting from 2-indanone. Knorr-type reaction of oximes derived from benzyl or tert-butyl acetoacetate with 2-indanone and zinc dust in propionic acid gave good yields of indenopyrroles. Treatment with N-chlorosuccinimide then gave 8-chloro derivatives, and these reacted with 5-unsubstituted pyrroles to give dipyrroles incorporating the fused indene unit. Hydrogenolysis of the benzyl ester protective groups afforded the related dicarboxylic acids, but condensation with a dipyrrylmethane dialdehyde under MacDonald "2 + 2" reaction conditions gave poor yields of the targeted indenoporphyrins. However, when an indene-fused dipyrrole was converted into the corresponding dialdehyde with TFA-trimethyl orthoformate and then reacted with a dipyrrylmethane dicarboxylic acid, an indenoporphyrin was isolated in 26% yield. The porphyrin gave a highly modified UV-vis absorption spectrum with three strong bands showing up in the Soret region and a series of Q bands that extended beyond 700 nm. The proton NMR spectrum also showed a significantly reduced diamagnetic ring current where the meso-protons gave resonances near 9.3 ppm instead of typical porphyrin values of 10 ppm. Nickel(II), copper(II), and zinc complexes were also prepared, and these exhibited unusual UV-vis absorption spectra with bathochromically shifted Soret and Q absorptions. The diamagnetic nickel(II) and zinc complexes also showed reduced diatropic character compared to typical nickel(II) and zinc porphyrins.

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“…4). 19,20 In 1985, they reported that condensation of tertbutoxycarbonyl and benzyloxycarbonyl chiral amino acids with 5a yielded picket-fence porphyrins bearing chiral protected pickets 5d-f. After deprotection, porphyrins 5g-h were isolated, and strapped using different diacyl chlorides affording the so-called ''gyroscope'' and bis-ansa porphyrins. 21 Studies concerning the latter will be discussed in section 5.5.…”

Section: Double Faced Picket Porphyrinsmentioning

confidence: 99%

Enantioselective epoxidation of olefins with chiral metalloporphyrin catalysts

et al. 2005

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The intent of this tutorial review is to cover the recent progress accomplished in iron and manganese porphyrin-catalyzed enantioselective epoxidation of terminal olefins. The literature is covered up to the beginning of 2005. In the first part of the manuscript, we will present the results obtained with simple catalysts in the early eighties, before describing the pickets and strapped series reported more recently. We will also place a special emphasis on the biomimetic approach that oriented most of this research throughout the years. As a conclusion, we will demonstrate that easy-to-prepare porphyrin catalysts should play an important role in the future and should compete with other well-known, successful systems. Among those, the popular titanium tartrate-catalyzed Sharpless-Katsuki asymmetric epoxidation allows the conversion of allylic alcohols to chiral epoxides with high enantiomeric excesses and high conversion. We will also cite the chiral metallosalen complexes independently reported by Jacobsen and Katsuki in 1990. Using manganese-salens, cis-1,2-disubstituted, trisubstituted and some tetrasubstituted olefins are efficiently epoxidized with high enantiomeric excess. However, they suffer from two major drawbacks. They often require low temperature for the epoxidation of monosubstituted (57% ee for styrene at 5 degrees C; 80% at -78 degrees C). More importantly, they proceed with low turnover numbers, TON (TON approximately 40 for styrene). More recently, a new approach involving metal-free chiral dioxiranes was also reported. In some cases, they constitute an interesting alternative to the more common systems previously discussed. Compared to the three pre-cited systems, chiral metalloporphyrins allow the enantioselective epoxidation of unfunctionalized terminal olefins with high enantiomeric excess (>97% ee for styrene) and impressive turnover numbers (>16000) when PhIO is used as oxidant. These results highlight the remarkable potential of porphyrin-based catalysts.

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Synthèse de méso-α,γ bis(diamino-2,6 phényl) porphyrines

Cited by 17 publications

References 8 publications

Synthesis of 5,15-Diaryltetrabenzoporphyrins

Synthesis of 5,15-Diaryltetrabenzoporphyrins

Synthesis of Indenoporphyrins, Highly Modified Porphyrins with Reduced Diatropic Characteristics

Enantioselective epoxidation of olefins with chiral metalloporphyrin catalysts

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