Facile synthesis of a B,D-tetradehydrocorrin and rearrangement to bacteriochlorins

Aravindu, Kunche; Krayer, Michael; Kim, Han-Je; Lindsey, Jonathan S.

doi:10.1039/c1nj20027e

Cited by 15 publications

(14 citation statements)

References 49 publications

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“…13 Mild acid catalysis with Yb(OTf) 3 instead of BF 3 ÁO(Et) 2 affords the tetradehydrocorrin selectively. 24 Such tetradehydrocorrins are known to undergo rearrangement upon acid catalysis stronger than Yb(OTf) 3 to form the bacteriochlorin. 24 Treatment of tetradehydrocorrin 1 with NBS afforded the brominated derivative Br-1, where the bromine is located at the meso-position distal to the A-D ring junction (Scheme 2).…”

Section: Njc Papermentioning

confidence: 99%

“…24 Such tetradehydrocorrins are known to undergo rearrangement upon acid catalysis stronger than Yb(OTf) 3 to form the bacteriochlorin. 24 Treatment of tetradehydrocorrin 1 with NBS afforded the brominated derivative Br-1, where the bromine is located at the meso-position distal to the A-D ring junction (Scheme 2). 24 Here, treatment of Br-1 with BF 3 ÁO(Et) 2 gave the corresponding meso-brominated bacteriochlorin BrBC-2.…”

Section: Njc Papermentioning

confidence: 99%

“…24 Treatment of tetradehydrocorrin 1 with NBS afforded the brominated derivative Br-1, where the bromine is located at the meso-position distal to the A-D ring junction (Scheme 2). 24 Here, treatment of Br-1 with BF 3 ÁO(Et) 2 gave the corresponding meso-brominated bacteriochlorin BrBC-2. The BrBC-2 was previously identified in a complex mixture containing other bromobacteriochlorins as shown for case B in Scheme 1, but was not isolated in pure form.…”

Section: Njc Papermentioning

confidence: 99%

“…Compounds 10-bromo-1H,22H,24H-7,8,17,18-tetradehydro-1-(1,1-dimethoxymethyl)-3,3,13,13-tetramethyl-7,17-di-p-tolylcorrin (Br-1), 24 2-{4-[2-(triisopropylsilyl)ethynyl]phenyl}-4,4,5,5-tetramethyl-1, 3,2-dioxaborolane (2), [35][36][37] 2-[4-(2-(tert-butoxycarbonyl)ethyl)phenyl]-3,3,4,4-tetramethyl-1,3,2-dioxaborolane (5), 42 4-(tert-butyldiphenyl-silyloxy)aniline ( 10), 82 and several bacteriochlorins (BrBC-3, 19 BrBC-4, 265 BrBC-7, 14 BrBC-8, 16 BrBC-20, 41 BrBC-22, 42 and BC-24 14 ) were prepared following literature procedures. Bacteriochlorins BC-9 and BC-10 were reported in the companion paper.…”

Section: Non-commercial Compoundsmentioning

confidence: 99%

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Meso bromination and derivatization of synthetic bacteriochlorins

et al. 2022

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Section: Njc Papermentioning

confidence: 99%

Section: Njc Papermentioning

confidence: 99%

Section: Njc Papermentioning

confidence: 99%

Section: Non-commercial Compoundsmentioning

confidence: 99%

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Meso bromination and derivatization of synthetic bacteriochlorins

et al. 2022

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“…The gem-dimethyl group secures the pyrroline ring from adventitious oxidation that would lead to unsaturated products (i.e., chlorins and porphyrins). 10,11,22 As a general rule, the use of BF 3 ÁOEt 2 at modest concentrations in CH 3 CN typically provides a mixture of two if not all three macrocycles, but with 140 mM BF 3 ÁOEt 2 and 18 mM dihydrodipyrrin-acetal, the HBC-type macrocycle is the dominant macrocyclic product (20-30% yield). 8,9,15,17,[19][20][21] A key aspect of the self-condensation of a dihydrodipyrrinacetal is that different acidic conditions (acid composition and concentration) and dihydrodipyrrin-acetal concentrations can lead to distinct outcomes with regards to the macrocycles formed: a free base 5-unsubstituted bacteriochlorin (HBC-type macrocycle), a free base 5-methoxybacteriochlorin (MeOBCtype macrocycle), a free base B,D-tetradehydrocorrin (TDC-type macrocycle).…”

Section: Introductionmentioning

confidence: 99%

Synthesis and photophysical characteristics of 2,3,12,13-tetraalkylbacteriochlorins

et al. 2016

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Bacteriochlorins absorb strongly in the near-infrared spectral region and hence are of great interest across the field of photochemistry. The established de novo self-condensation of a dihydrodipyrrinacetal has afforded stable bacteriochlorins bearing a variety of b-pyrrolic substituents, but the route was incompatible with the presence of two alkyl groups. The lacuna stemmed from the instability of the dialkyl-substituted dihydrodipyrrin-acetal. Here, two dihydrodipyrrin-carboxaldehydes, each bearing a tert-butoxycarbonyl group at the pyrrole a-position, were prepared and found to be stable to routine handling. Each ester-substituted dihydrodipyrrin-carboxaldehyde in acid underwent in situ ester cleavage and ensuing self-condensation to provide the corresponding 2,3,12,13-tetraalkylbacteriochlorin.The alkyl groups examined include methyl and methyl acetate. Such synthetic bacteriochlorins, while previously unknown, provide valuable models of the natural chromophores. The absorption and fluorescence characteristics of the tetraalkylbacteriochlorins are generally typical for this genre of macrocycle. The X-ray structure of the tetramethylbacteriochlorin reveals that the pyrrolinic (reduced) rings are modestly more twisted out-of-plane (torsional angle B111) than those of the nearly planar (torsional angle B11) parent bacteriochlorin that lacks pyrrolic tetraalkyl groups. The resonance Raman spectrum of the tetramethylbacteriochlorin is also far richer in the low-to mid-frequency region than that of the unsubstituted analogue, but like the unsubstituted counterpart, is far sparser in the highfrequency region than that of native bacteriochlorophyll. Access to tetraalkylbacteriochlorins constitutes one step on the path from the most simple, fully unsubstituted bacteriochlorin to the fully decorated, natural bacteriochlorophylls.

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Oxidative Formation and Redox Properties of 9‐Methylisocorroles

et al. 2019

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Cationic nickel(II), palladium(II), and copper(II) isocorrole complexes were obtained from linear tetrapyrrolic 2,2′bidipyrrin precursors by metal-templated oxidative macrocyclization reactions using silver(I) tetrafluoroborate as the oxidant in 40-69 % yield. The new compounds were characterized by optical and resonance methods. Two products from overoxidation and attack of nucleophiles were identified by means of single-crystal X-ray diffraction, elucidating possible H atom [a] .62, triclinic, space group P1 , a = 11.4751 (2) Å, b = 12.2697(2) Å, c = 15.8838(3) Å, α = 96.196(2)°, = 102.527(2)°, γ = 116.272(2)°, V = 1903.75(7) Å 3 , Z = 2, ρ calc = 1.255 g cm -3 , μ(Cu-K α ) = 1.011 mm -1 , R 1 [I > 2σ(I)] = 0.0479, wR 2 (all data) = 0.1408. Crystal Data for 15: C 46 H 52 CuN 4 , M = 724.45, triclinic, space group P1 , a = 11.1150(5) Å, b = 12.3637(7) Å, c = 16.2701(6) Å, α = 96.602(4)°, = 102.207(3)°, γ = 115.355(5)°, V = 1920.6(2) Å 3 , Z = 2, ρ calc = 1.253 g cm -3 , μ(Cu-K α ) = 1.076 mm -1 , R 1 [I > 2σ(I)] = 0.0563, wR 2 (all data) = 0.1615. Crystal Data for 30: C 92 H 100 F 12 N 8 Ni 2 Sb 2 + 3.566×(CH 2 Cl 2 ) M = 2209.55, triclinic, space group P1, a = 17.4048(8) Å, b = 17.5535(8) Å, c = 19.7399(8) Å, α = 84.942(4)°, = 68.619(4)°, γ = 60.298(4)°, V = 4846.0(4) Å 3 , Z = 2, ρ calc = 1.510 g cm -3 , μ(Cu-K α ) = 7.190 mm -1 , R 1 [I > 2σ(I)] = 0.0628, wR 2 (all data) = 0.1701. Crystal Data for 31: C 38 H 50 N 4 NiO 2 , M = 653.53, monoclinic, space group P2 1 /c, a = 13.3144(3) Å, b = 17.0511(5) Å, c = 15.0318(3) Å, = 100.396(2)°, V = 3356.58(14) Å 3 , Z = 4, ρ calc = 1.293 g cm -3 , μ(Cu-K α ) = 1.133 mm -1 , R 1 [I > 2σ(I)] = 0.0395, wR 2 (all data) = 0.1090. CCDC 1938499 (for 13), 1938498 (for 15), 1056473 (for 30), and 1938500 (for 31) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre.

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Facile synthesis of a B,D-tetradehydrocorrin and rearrangement to bacteriochlorins

Cited by 15 publications

References 49 publications

Meso bromination and derivatization of synthetic bacteriochlorins

Meso bromination and derivatization of synthetic bacteriochlorins

Synthesis and photophysical characteristics of 2,3,12,13-tetraalkylbacteriochlorins

Oxidative Formation and Redox Properties of 9‐Methylisocorroles

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