A straightforward approach to carborane-substituted BODIPY derivatives via nucleophilic aromatic substitution: Synthesis and photodynamic properties

Synthesis and Regioselective Functionalization of Tetrafluorobenzo-[α]-Fused BOPYPY Dyes

“…Nucleophilic substitutions of halogenated BODIPY derivatives and other chromophores are a convenient methodology for the introduction of various types of nucleophiles, including S-, N-, O-, and C-centered examples, onto a chromophore to modulate its chemical and photophysical properties. , In particular, the introduction of aromatic fluorines provides a useful strategy for direct conjugation of molecules via S N Ar reactions, under mild conditions. These reactions normally occur via a concerted two-step addition–elimination mechanism by nucleophilic attack on the electron-deficient benzo ring.…”

Physico‐chemical Properties and Anticancer Activity of Carborane‐BODIPY Conjugates: A Review

“…More recently 2022, a new class of amphiphilic and water soluble anionic carborane derivatives of 4,4‐difluoro‐4‐bora‐3a,4a‐diaza‐s‐indacene (BODIPY) 125 – 130 were efficiently synthesized via nucleophilic aromatic substitution of p ‐fluorine atom in meso‐8‐pentafluorophenyl‐substituted BODIPYs with carborane S‐nucleophiles (Scheme 24). [68] The newly synthesized conjugates retained the advantageous photochemical properties of BODIPY such as high fluorescence and generation of singlet oxygen whereas the carborane moiety increased the values of binding constant (Kb) in complexes with albumin. The binding constants (Kb) values of carborane‐BODIPY conjugates 125 , 129 and 130 showed in the range (1–3.5)×10 5 M −1 as based on absorption and fluorescence spectra of the fluorophore in the presence of BSA.…”

BODIPY derivatives modified with carborane clusters: synthesis, characterization and DFT studies

“…49,50 Similar reactions are usually employed for the functionalization of macrocyclic compounds such as porphyrins, chlorins, phthalocyanines and BODIPYs. 15,37,[51][52][53] It was found that the reactions of BODIPYs 4, 5 and 7 with the corresponding mercaptocarboranes proceeded efficiently for 1 h in DMF in the presence of NaOAc for compounds 4 and 5 and in the presence of K 2 CO 3 for compound 7 providing the desired BODIPYs 8-10 decorated with three carborane clusters in 70-81% yields (Scheme 1).…”

“…25,26 In recent decades, BODIPYs containing carborane clusters have been deeply involved in medical research as dual sensitizers for PDT and BNCT [27][28][29][30][31][32][33] as well as for the design of photoluminescent materials. 34 In the course of our studies directed on the development of carborane-containing PSs for PDT and BNCT we recently reported the synthesis of carborane-BODIPY derivatives [35][36][37] and found that these compounds, being negligibly cytotoxic in the dark, potently induced lipid peroxidation and rapid (within minutes) cell death of HCT116 colon adenocarcinoma cells upon photoactivation. 37 In this article a series of BODIPY derivatives containing two boron clusters were prepared by bromo substitution in 3,5-dibromo-8-pentafluorophenyl-BODIPY with carborane S-nucleophiles.…”

“…34 In the course of our studies directed on the development of carborane-containing PSs for PDT and BNCT we recently reported the synthesis of carborane-BODIPY derivatives [35][36][37] and found that these compounds, being negligibly cytotoxic in the dark, potently induced lipid peroxidation and rapid (within minutes) cell death of HCT116 colon adenocarcinoma cells upon photoactivation. 37 In this article a series of BODIPY derivatives containing two boron clusters were prepared by bromo substitution in 3,5-dibromo-8-pentafluorophenyl-BODIPY with carborane S-nucleophiles. Moreover we managed to prepare boron-enriched carborane BODIPYs by the modification of 3,5-dicarborane-substituted BODIPYs via the S N Ar substitution reactions of the para-fluorine atom in the pentafluorophenyl BODIPY substituent with a carborane nucleophile.…”