Synthesis and Electronic Properties of Regioisomerically Pure Oxochlorins

Taniguchi, Masahiko; Kim, † Han-Je; Ra, Doyoung; Schwartz, Jennifer K.; Kirmaier, Christine; Hindin, Eve; Diers, James R.; Prathapan, Sreedharan; Bocian, David F.; Holten, Dewey; Lindsey, Jonathan S.

doi:10.1021/jo025843i

Cited by 64 publications

(124 citation statements)

References 76 publications

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“…Further chromatography of the second fraction gave 17-OH as a red-brown solid (20 mg, 10%). The data for 17 and 17-OH (mp, 1 H NMR, 13 C NMR, and FAB-MS) were consistent with those obtained from samples prepared via reduction with Zn/HCO 2 NH 4 . /HCO 2 H-Following a general procedure,32 a solution of 16 (0.101 g, 0.400 mmol) in ethanol (3.6 mL) was treated with formic acid (0.9 mL) and zinc dust (0.65 g, 10 mmol).…”

Section: Synthesis Of 16 In Thf With Tbaf-followingsupporting

confidence: 80%

“…Chromatography [silica, hexanes/ethyl acetate (3:1)] afforded a brown oil (3.25 g, 43%). The data ( 1 H NMR, 13 C NMR, and FAB-MS) were consistent with those obtained from samples prepared via the solventless method. The mixture was diluted with ethyl acetate and filtered.…”

Section: Synthesis Of 16 In Thf With Tbaf-followingsupporting

confidence: 79%

“…1 H NMR (400 MHz) and 13 C NMR (100 MHz) spectra were collected at room temperature in CDCl 3 unless noted otherwise. Melting points are uncorrected.…”

Section: Generalmentioning

confidence: 99%

“…Although chlorophylls and bacteriochlorophylls lack the geminal dialkyl motif, synthetic analogues that contain a geminal dialkyl group in the pyrroline ring exhibit characteristic chlorin or bacteriochlorin features and are quite stable compounds. [10][11][12][13][14][15] The de novo syntheses that we developed of chlorins, which drew heavily on methods established in the total synthesis of bonellin, 16,17 are shown in Scheme 1. Each de novo synthesis involves the convergent joining of an Eastern half and a Western half.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of hydrodipyrrins tailored for reactivity at the 1- and 9-positions

et al. 2007

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A collection of 33 hydrodipyrrins (9 targets, 21 intermediates, and 3 byproducts) has been prepared. The hydrodipyrrins (dihydrodipyrrins, tetrahydrodipyrrins, and hexahydrodipyrrins) contain a pyrrole ring and a geminal-dimethyl substituted 1-pyrroline (or pyrrolidine) ring. The α-substituents on the pyrrole ring (H, Br, CHO) and pyrroline ring (H, CH 3 , CH(OR) 2 , OMe, SMe) provide different reactivity combinations (Nu − , E + ) and 0, 1, or 2 carbon atoms (which can give rise to the bridging meso-carbons in hydroporphyrins). Straightforward access to various hydrodipyrrins should facilitate development of syntheses of diverse hydroporphyrins.

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Section: Synthesis Of 16 In Thf With Tbaf-followingsupporting

confidence: 80%

Section: Synthesis Of 16 In Thf With Tbaf-followingsupporting

confidence: 79%

“…1 H NMR (400 MHz) and 13 C NMR (100 MHz) spectra were collected at room temperature in CDCl 3 unless noted otherwise. Melting points are uncorrected.…”

Section: Generalmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Synthesis of hydrodipyrrins tailored for reactivity at the 1- and 9-positions

et al. 2007

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“…HCOONH 4 (252 g, 3.90 mol) and zinc dust (261 g, 3.90 mol) were added and resulting suspension was vigorously stirred using a mechanical stirrer (see note iv below). After 2 h, GC analysis did not show any starting hexanone (5) or intermediate N-oxide (6). The mixture was filtered through filter paper and the filter cake was washed with ethyl acetate (2500 mL).…”

Section: Direct Conversion Of 2 → 1 (040 Mol Scale)mentioning

confidence: 99%

Refined Synthesis of 2,3,4,5-Tetrahydro-1,3,3-trimethyldipyrrin, a Deceptively Simple Precursor to Hydroporphyrins

Ptaszek

Bhaumik

Kim

et al. 2005

Org. Process Res. Dev.

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109

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2,3,4,3, (1) is a crucial building block in the rational synthesis of chlorins and oxochlorins. The prior 5-step synthesis of 1 from pyrrole-2-carboxaldehyde (2) employed relatively simple and well-known reactions yet suffered from several drawbacks, including limited scale (≥ 0.5 g of 1 per run). A streamlined preparation of 1 has been developed that entails four steps: (i) nitro-aldol condensation of 2 and nitromethane under neat conditions to give 2-(2-nitrovinyl)pyrrole (3), (ii) reduction of 3 with NaBH 4 to give 2-(2-nitroethyl)pyrrole (4), (iii) Michael addition of 4 with mesityl oxide under neat conditions or at high concentration to give γ-nitrohexanonepyrrole 5, and (iv) reductive cyclization of 5 with zinc/ammonium formate to give 1. Several multistep transformations have been established, including the direct conversion of 2 → 1. The advantages of the new procedures include (1) fewer steps, (2) avoidance of several problematic reagents, (3) diminished consumption of solvents and reagents, (4) lessened reliance on chromatography, and (5) scalability. The new procedures facilitate the preparation of 1 at the multigram scale.

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Iron Porphyrin Chemistry

Walker¹,

Simonis²

2005

Encyclopedia of Inorganic Chemistry

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This article reviews most aspects of the chemistry of iron porphyrins, from Fe(0) to Fe(V), including occurrence and roles of natural iron porphyrins (hemes) and their synthetic analogs, structures and electron configurations of iron porphyrins of all oxidation and spin states, π electron configuration of the porphyrin ring, synthesis of metal‐free porphyrins and other related macrocycles, insertion of iron into free‐base porphyrins and related macrocycles, the properties, reactions, uses and biological relevance of iron(0), ‐(I), ‐(II) porphyrins (the latter with S = 0, 1, and 2 spin state possibilities), of iron(II) porphyrin π‐cation radicals, of iron(III) porphyrins (with S = 1/2, 3/2, and 5/2 spin state possibilities), of iron(III) porphyrin and corrole π‐cation radicals, of iron(IV) porphyrins (including five‐ and six‐coordinate ferryl (FeO) 2+ , iron(IV) phenyl, carbene and hydrazine complexes, and the bis‐methoxide complex) and a comparison of iron(IV) porphyrins to iron(III) porphyrin π‐cation radicals, of iron(IV) porphyrin π‐cation radicals, and of the possible existence of iron(V) porphyrins. Included in the Fe(II) part are sections on addition of ligands to four‐coordinate iron(II) porphyrins, including equilibrium binding constants, photodissociation of ligands from PFeL 2 complexes, binding of small molecules (O 2 , CO, NO, HNO) to 5‐coordinate iron(II) porphyrins and design of porphyrin ligands that will mimic the active sites of heme proteins such as myoglobin and hemoglobin, the cytochromes P450 and nitric oxide synthases, and the nitrophorins and guanylyl cyclases. Included in the iron(III) part are sections on both 5‐ and 6‐coordinate high‐spin complexes and their similarities and differences, bridged or through‐space magnetically coupled complexes of high‐spin iron(III) porphyrins with other metal complexes as possible models for cytochrome oxidase and the assimilatory sulfite reductases, coupled oxidation of hemes by hydrogen peroxide or its equivalent, and the relationship of this reactivity to the reactions of heme oxygenase, iron(III) porphyrins as reduction catalysts, and photochemistry of iron(III) porphyrins, possible electron configurations of low‐spin iron(III) porphyrins, the phenomenon and possible electronic consequences of ruffling of the porphinato core in iron(III) porphyrins, the preferred orientation of planar axial ligands bound to low‐spin iron(III) porphyrins, NO complexes of iron(III) porphyrins, reduction potentials, equilibrium constants and rates of axial‐ligand addition and exchange, kinetics of axial‐ligand rotation and porphyrin ring inversion, kinetics of reduction and autoreduction of iron(III) porphyrins, electron self‐exchange between low‐spin iron(III) and iron(II) porphyrins, synthetic ferriheme proteins, and synthesis of five‐coordinate low‐spin iron(III) porphyrins having σ‐alkyl or σ‐aryl groups as axial ligands. The iron(IV) and iron(IV) cation radical sections discuss the high‐valent states of cytochromes P450 and related enzymes.

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Synthesis and Electronic Properties of Regioisomerically Pure Oxochlorins

Cited by 64 publications

References 76 publications

Synthesis of hydrodipyrrins tailored for reactivity at the 1- and 9-positions

Synthesis of hydrodipyrrins tailored for reactivity at the 1- and 9-positions

Refined Synthesis of 2,3,4,5-Tetrahydro-1,3,3-trimethyldipyrrin, a Deceptively Simple Precursor to Hydroporphyrins

Iron Porphyrin Chemistry

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