Strongly Conjugated Hydroporphyrin Dyads: Extensive Modification of Hydroporphyrins’ Properties by Expanding the Conjugated System

Yu, Z. X.; Pancholi, Chirag; Bhagavathy, Ganga Viswanathan; Kang, Hyun Suk; Nguyen, Jamie K.; Ptaszek, Marcin

doi:10.1021/jo501041b

Cited by 38 publications

(92 citation statements)

References 91 publications

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“…Additional notable chlorin building blocks are shown in Scheme 94. The set includes the following: (1) chlorins with a single halo or ethyne ( 217 , 292 218 , 272 219 , 442 220 , 442 221 , 256 and 222 256 ); (2) oxochlorins with a single halo or ethyne ( 223 , 259 224 258 ); (3) chlorins with two halo or two ethynes ( 225 , 284 226 284 ); (4) chlorins with one halo and one ethyne ( 227 , 284 228 299 ); and (5) a chlorin with two bromo substituents and one ethyne ( 229 278 ).…”

Section: Smorgasbord Of Chlorinsmentioning

confidence: 99%

“…Chlorin 219 was prepared by reaction of an 8,9-dibromodipyrromethane bearing a 5- p -tolyl group ( 120f-Br 8,9 ; 442 analogue of 120c-Br 8,9 , Scheme 57) with Western half 118 ; subsequent Sonogashira coupling led to ethynylchlorin 220 . Chlorins 221 and 222 were prepared with a suitably diaryl-substituted Eastern half 119-Br 9 /OH and Western half 118 (Scheme 50); oxochlorins 223 and 224 were prepared likewise followed by oxidation of the 17-methylene unit (Scheme 54).…”

Section: Smorgasbord Of Chlorinsmentioning

confidence: 99%

“…Both the butadiynyl- and ethynyl-linked dyads show altered absorption spectra compared with those of the monomeric constituents. 442 …”

Section: Smorgasbord Of Chlorinsmentioning

confidence: 99%

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De NovoSynthesis of Gem-Dialkyl Chlorophyll Analogues for Probing and Emulating Our Green World

2015

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Woodward reported his infamous synthesis of chlorin e 6 trimethyl ester, a known synthetic precursor to chlorophyll a. [59][60][61][62][63][64]124 The work was posited on a half-century of intensive studies by many investigators in tetrapyrrole chemistry and began a decade after the close of Fischer's lifetime of research 125−128 (which included an uncompleted synthetic program directed toward chlorophylls 15 ). Indeed, "he read all the umpteen papers on the chlorophylls written by Willstaẗter and Fischer, including the experimental parts." 129 The Woodward synthesis of chlorin e 6 trimethyl ester required 46 steps, of which 24 were spent on converting the sole precursor, Knorr's pyrrole, to the four pyrroles destined to form rings A−D; 7 additional steps accrued to obtain the dipyrromethanes that constitute the Eastern and Western halves (Scheme 13, the step numbers are identical to those shown in ref 64.). The first step formed the Knorr pyrrole (in several kg quantities), the next 24 steps were divided into four parallel paths, whereas the remaining 21 steps proceeded in linear fashion. Remarkable features of the synthesis include the directed intramolecular joining (via an imine) of the Eastern and Western halves (step 33), construction of the acrylate Scheme 10. Hydrogenation of a Porphyrin to Form a Chlorin Scheme 11. Representative meso-Tetraarylchlorins Scheme 12. Methyl Pyropheophorbide a

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Section: Smorgasbord Of Chlorinsmentioning

confidence: 99%

Section: Smorgasbord Of Chlorinsmentioning

confidence: 99%

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De NovoSynthesis of Gem-Dialkyl Chlorophyll Analogues for Probing and Emulating Our Green World

2015

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“…34 The steric hindrance caused by the methoxy group at the 5-position causes Pd-mediated coupling with the 3,13-dibromobacteriochlorin to proceed regioselectively at the 13-position with one equivalent of the ethyne. 24,35,36 Therefore, the Sonogashira coupling reaction of 3 with methyl 4-ethynylbenzoate ( 4 ) regioselectively proceeded at the 13-position of the macrocycle to give ethynylbacteriochlorin 5 in 42% yield (Scheme 1). Further reaction of 5 with ethyne 6 in the presence of Pd(PPh 3 ) 2 Cl 2 and Et 3 N in DMF at 80 °C gave unsymmetrically substituted bacteriochlorin 7 .…”

Section: Resultsmentioning

confidence: 99%

Bioconjugatable, PEGylated hydroporphyrins for photochemistry and photomedicine. Narrow-band, near-infrared-emitting bacteriochlorins

et al. 2016

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Synthetic bacteriochlorins absorb in the near-infrared (NIR) region and are versatile analogues of natural bacteriochlorophylls. The utilization of these chromophores in energy sciences and photomedicine requires the ability to tailor their physicochemical properties, including the incorporation of units to impart water solubility. Herein, we report the synthesis, from two common bacteriochlorin building blocks, of five wavelength-tunable, bioconjugatable and water-soluble bacteriochlorins along with two non-bioconjugatable benchmarks. Each bacteriochlorin bears short polyethylene glycol (PEG) units as the water-solubilizing motif. The PEG groups are located at the 3,5-positions of aryl groups at the pyrrolic β-positions to suppress aggregation in aqueous media. A handle containing a single carboxylic acid is incorporated to allow bioconjugation. The seven water-soluble bacteriochlorins in water display Qy absorption into the NIR range (679–819 nm), sharp emission (21–36 nm full-width-at-half-maximum) and modest fluorescence quantum yield (0.017–0.13). Each bacteriochlorin is neutral (non-ionic) yet soluble in organic (e.g., CH2Cl2, DMF) and aqueous solutions. Water solubility was assessed using absorption spectroscopy by changing the concentration ∼1000-fold (190–690 µM to 0.19–0.69 µM) with a reciprocal change in pathlength (0.1–10 cm). All bacteriochlorins showed excellent solubility in water, except for a bacteriochlorin–imide that gave slight aggregation at higher concentrations. One bacteriochlorin was conjugated to a mouse polyclonal IgG antibody for use in flow cytometry with compensation beads for proof-of-principle. The antibody conjugate of B2-NHS displayed a sharp signal upon ultraviolet laser excitation (355 nm) with NIR emission measured with a 730/45 nm bandpass filter. Overall, the study gives access to a set of water-soluble bacteriochlorins with desirable photophysical properties for use in multiple fields.

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“…A more pronounced bathochromic shift than observed herein appears to require more extensive modification of the macrocyclic structure. The research reported here predated and somewhat inspired our recent studies on strongly conjugated hydroporphyrin arrays, which appears to be an efficient way to bathochromically shift the chlorin absorption [27]. …”

Section: Resultsmentioning

confidence: 99%

Progress towards synthetic chlorins with graded polarity, conjugatable substituents, and wavelength tunability

Gauger

Muthukumaran

et al. 2015

J. Porphyrins Phthalocyanines

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Advances in chlorin synthetic chemistry now enable the de novo preparation of diverse chlorin-containing molecular architectures. Five distinct molecular designs have been explored here, including hydrophobic bioconjugatable (oxo)chlorins; a hydrophilic bioconjugatable chlorin; a trans-ethynyl/iodochlorin building block; a set of chlorins bearing electron-rich (methoxy, dimethylamino, methylthio) groups at the 3-position; and a set of ten 3,13-disubstituted chlorins chiefly bearing groups with extended π-moieties. Altogether 23 new chlorins (17 targets, 6 intermediates) have been prepared. The challenge associated with molecular designs that encompass the combination of “hydrophilic, bioconjugatable and wavelength-tunable” chiefly resides in the nature of the hydrophilic unit.

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Strongly Conjugated Hydroporphyrin Dyads: Extensive Modification of Hydroporphyrins’ Properties by Expanding the Conjugated System

Cited by 38 publications

References 91 publications

De NovoSynthesis of Gem-Dialkyl Chlorophyll Analogues for Probing and Emulating Our Green World

De NovoSynthesis of Gem-Dialkyl Chlorophyll Analogues for Probing and Emulating Our Green World

Bioconjugatable, PEGylated hydroporphyrins for photochemistry and photomedicine. Narrow-band, near-infrared-emitting bacteriochlorins

Progress towards synthetic chlorins with graded polarity, conjugatable substituents, and wavelength tunability

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