Control of Oligomerization and Oxidation Steps in the Synthesis of Tris(pentafluorophenyl)corrole

Blumenfeld, Carl; Fisher, Katherine; Henling, Lawrence M.; Grubbs, Robert H.; Gray, Harry B.; Virgil, Scott C.

doi:10.1002/ejoc.201500276

Cited by 16 publications

(10 citation statements)

References 22 publications

(1 reference statement)

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“…It is noteworthy to add that one of the pre-1999 serendipitous syntheses of A 3 -corroles was also performed in CH 2 Cl 2 with TFA as a catalyst . Very recently, the reaction of aldehyde 38 with pyrrole ( 37 ) was investigated again by the joint efforts of Virgil, Grubbs, and Gray . These authors reanalyzed both steps (i.e., the cascade of electrophilic aromatic substitution and macrocyclization).…”

Section: Meso-substituted A3-corrolesmentioning

confidence: 99%

Synthesis of Corroles and Their Heteroanalogs

2016

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Corroles have come a long way from being a curiosity to being a mainstream research topic. They are now regularly synthesized in numerous research laboratories worldwide with diverse specific aims in mind. In this review we present a comprehensive description of corroles' synthesis, developed both before and after 1999. To aid the investigator in developing synthetic strategies, some of the sections culminate in tables containing comparisons of various methodologies leading to meso-substituted corroles. The remaining challenges are delineated. In the second part of this review, we also describe the syntheses of isocorroles and heteroanalogs of corroles such as triazacorroles (corrolazines), 10-heterocorroles, 21-heterocorroles, 22-heterocorroles, N-confused corroles, as well as norcorroles. The review is complemented with a short outlook.

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Section: Meso-substituted A3-corrolesmentioning

confidence: 99%

Synthesis of Corroles and Their Heteroanalogs

2016

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“…The most stable corrole reported so far is H 3 (tpfc) (1, Scheme ), which contains three C 6 F 5 groups on the meso-positions of the corrole skeleton. These meso-substituents are apparently also responsible for the very high selectivity obtained during electrophilic substitutions on the macrocycle, , for reasons that have not being fully addressed so far.…”

Section: Introductionmentioning

confidence: 99%

Intriguing Physical and Chemical Properties of Phosphorus Corroles

et al. 2016

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The fluorescence intensity of phosphorus corroles increases upon meso-aryl C-F/C-H and P-OH/P-F substitutions, the latter affects corrole-centered redox processes more than C-H/C-F substitution on the corrole's skeleton, and the presence of F atoms allows for the first experimental insight into the electronic structures of oxidized corroles. Experimental and theoretical methodologies reveal that mono- but not bis-chlorosulfonation of the corrole skeleton is under kinetic control. Selective introduction of heavy atoms leads to complexes that are phosphorescent at room temperature.

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“…Corroles have received a great deal of attention in recent years (10)(11)(12)(13), owing to dramatic advances in methods for their preparation (14)(15)(16)(17)(18)(19)(20)(21)(22)(23)(24)(25)(26)(27)(28)(29)(30)(31). Of interest here is a gallium(III) complex, 1 [Ga(tpfc)] (32)(33)(34)(35), where tpfc represents the trianion of 5,10,15-tris(pentafluorophenyl)corrole [H 3 (tpfc)].…”

mentioning

confidence: 99%

Cellular uptake and anticancer activity of carboxylated gallium corroles

Pribisko

Palmer²,

Grubbs

et al. 2016

Proc. Natl. Acad. Sci. U.S.A.

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We report derivatives of gallium(III) tris(pentafluorophenyl)corrole, 1 [Ga(tpfc)], with either sulfonic (2) or carboxylic acids (3, 4) as macrocyclic ring substituents: the aminocaproate derivative, 3 [Ga(ACtpfc)], demonstrated high cytotoxic activity against all NCI60 cell lines derived from nine tumor types and confirmed very high toxicity against melanoma cells, specifically the LOX IMVI and SK-MEL-28 cell lines. The toxicities of 1, 2, 3, and 4 [Ga(3-ctpfc)] toward prostate (DU-145), melanoma (SK-MEL-28), breast (MDA-MB-231), and ovarian (OVCAR-3) cancer cells revealed a dependence on the ring substituent: IC 50 values ranged from 4.8 to >200 μM; and they correlated with the rates of uptake, extent of intracellular accumulation, and lipophilicity. Carboxylated corroles 3 and 4, which exhibited about 10-fold lower IC 50 values (<20 μM) relative to previous analogs against all four cancer cell lines, displayed high efficacy (E max = 0). Confocal fluorescence imaging revealed facile uptake of functionalized gallium corroles by all human cancer cells that followed the order: 4 >> 3 > 2 >> 1 (intracellular accumulation of gallium corroles was fastest in melanoma cells). We conclude that carboxylated gallium corroles are promising chemotherapeutics with the advantage that they also can be used for tumor imaging.

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Control of Oligomerization and Oxidation Steps in the Synthesis of Tris(pentafluorophenyl)corrole

Cited by 16 publications

References 22 publications

Synthesis of Corroles and Their Heteroanalogs

Synthesis of Corroles and Their Heteroanalogs

Intriguing Physical and Chemical Properties of Phosphorus Corroles

Cellular uptake and anticancer activity of carboxylated gallium corroles

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