@article{mroz_bhaumik_dogutan_aly_kamal_khalid_kee_bocian_holten_lindsey_et al._2009, title={Imidazole metalloporphyrins as photosensitizers for photodynamic therapy: Role of molecular charge, central metal and hydroxyl radical production}, volume={282}, ISSN={["1872-7980"]}, DOI={10.1016/j.canlet.2009.02.054}, abstractNote={The in vitro photodynamic therapy activity of four imidazole-substituted metalloporphyrins has been studied using human (HeLa) and mouse (CT26) cancer cell lines: an anionic Zn porphyrin and a homologous series of three cationic Zn, Pd or InCl porphyrins. A dramatic difference in phototoxicity was found: Pd cationic>InCl cationic>Zn cationic>Zn anionic. HeLa cells were more susceptible than CT26 cells. Induction of apoptosis was demonstrated using a fluorescent caspase assay. The anionic Zn porphyrin localized in lysosomes while the cationic Zn porphyrin localized in lysosomes and mitochondria, as assessed by fluorescence microscopy. Studies using fluorescent probes suggested that the cationic Pd porphyrin produced more hydroxyl radicals as the reactive oxygen species. Thus, the cationic Pd porphyrin has high potential as a photosensitizer and gives insights into characteristics for improved molecular designs.}, number={1}, journal={CANCER LETTERS}, author={Mroz, Pawel and Bhaumik, Jayeeta and Dogutan, Dilek K. and Aly, Zarmeneh and Kamal, Zahra and Khalid, Laiqua and Kee, Hooi Ling and Bocian, David F. and Holten, Dewey and Lindsey, Jonathan S. and et al.}, year={2009}, month={Sep}, pages={63–76} }
 @article{dogutan_ptaszek_lindsey_2008, title={Rational or statistical routes from 1-acyldipyrromethanes to meso-substituted porphyrins. Distinct patterns, multiple pyridyl substituents, and amphipathic architectures}, volume={73}, ISSN={["0022-3263"]}, DOI={10.1021/jo800588n}, abstractNote={New methodology is described for the synthesis of porphyrins bearing four (A 4, cis-A 2B 2, cis-ABC 2, trans-A 2B 2) or fewer (A, cis-AB, cis-A 2, trans-A 2) meso substituents. The method entails condensation of two 1-acyldipyrromethanes in the presence of a metal salt (MgBr 2, 3 mol equiv) and a noncoordinating base (DBU, 10 mol equiv) in a noncoordinating solvent (toluene) with heating (conventional or microwave irradiation) and exposure to air. The rational synthesis of trans-A 2B 2- or trans-A 2-porphyrins was achieved via condensation of two identical 1-acyldipyrromethanes. The statistical synthesis of various meso-substituted porphyrins was achieved via condensation of two nonidentical 1-acyldipyrromethanes. Both routes possess attractive features including (1) no scrambling, (2) good yield (up to 60%) at high concentration (100 mM) for the macrocycle-forming step, (3) reasonable scope (aryl, heteroaryl, alkyl, or no substituent), (4) short reaction time ( approximately 2 h) via microwave irradiation, (5) magnesium porphyrins as the products, which easily undergo demetalation, and (6) facile chromatographic purification. A key advantage of the statistical route is to obtain a cis-substituted porphyrin without the corresponding trans isomer. For example, reaction of an A/B-substituted 1-acyldipyrromethane and the fully unsubstituted 1-formyldipyrromethane gave the magnesium chelates of three porphyrins: the trans-A 2B 2-porphyrin, the "hybrid" cis-AB-porphyrin, and porphine (no trans-AB-porphyrin can form), which were readily demetalated and separated as the free base species. Altogether 26 1-acyldipyrromethanes and 26 target porphyrins have been prepared, including many with two different pyridyl substituents. One set of amphipathic porphyrins includes cis-A 2B 2- or cis-A 2BC-porphyrins wherein A = pentyl and B/C = pyridyl ( o-, m-, p-). Taken together, the rational and statistical routes enable facile conversion of readily available 1-acyldipyrromethanes to diverse porphyrins bearing 1-4 meso substituents for which access is limited via other methods.}, number={16}, journal={JOURNAL OF ORGANIC CHEMISTRY}, author={Dogutan, Dilek Kiper and Ptaszek, Marcin and Lindsey, Jonathan S.}, year={2008}, month={Aug}, pages={6187–6201} }
 @article{dogutan_ptaszek_lindsey_2007, title={Direct synthesis of magnesium porphine via 1-formyldipyrromethane}, volume={72}, ISSN={["0022-3263"]}, DOI={10.1021/jo070532z}, abstractNote={The reaction of 1-formyldipyrromethane (100 mM) in toluene at 115 degrees C containing DBU (10 mol equiv) and MgBr2 (3 mol equiv) in the presence of air affords the magnesium chelate Mg(II) porphine in 30-40% yield. The advantages of the new method include simplicity, high concentration, chromatography-free purification, gram-scale synthesis, and avoidance of the poorly soluble free base porphine. Mg(II) porphine exhibits good solubility in common organic solvents and is a valuable core scaffold for derivatization.}, number={13}, journal={JOURNAL OF ORGANIC CHEMISTRY}, author={Dogutan, Dilek Kiper and Ptaszek, Marcin and Lindsey, Jonathan S.}, year={2007}, month={Jun}, pages={5008–5011} }
 @article{dogutan_zaidi_thamyongkit_lindsey_2007, title={New route to ABCD-porphyrins via bilanes}, volume={72}, ISSN={["1520-6904"]}, DOI={10.1021/jo701294d}, abstractNote={A new strategy for preparing porphyrins that bear up to four different meso-substituents (ABCD-porphyrins) relies on two key reactions. One key reaction entails a directed synthesis of a 1-protected 19-acylbilane by acid-catalyzed condensation at high concentration (0.5 M) of a 1-acyldipyrromethane and a 9-protected dipyrromethane-1-carbinol (derived from a 9-protected 1-acyldipyrromethane). Three protecting groups (X) were examined, including thiocyanato, ethylthio, and bromo, of which bromo proved most effective. The bilanes were obtained in 72-80% yield, fully characterized, and examined by 15N NMR spectroscopy. The second key reaction entails a one-flask transformation of the 1-protected 19-acylbilane under basic, metal-templating conditions to give the corresponding metalloporphyrin. The reaction parameters investigated for cyclization of the bilane include solvent, metal salt, base, concentration, temperature, atmosphere, and time. The best conditions entailed the 1-bromo-19-acylbilane at 100 mM in toluene containing DBU (10 mol equiv) and MgBr2 (3 mol equiv) at 115 degrees C exposed to air for 2 h, which afforded the magnesium porphyrin in 65% yield. The magnesium porphyrin is readily demetalated to give the free base porphyrin. A stepwise procedure (which entailed treatment of the 1-(ethylthio)-19-acylbilane to oxidation, metal complexation, desulfurization, carbonyl reduction, and acid-catalyzed condensation) was developed but was much less efficient than the one-flask process. The new route to ABCD-porphyrins retains the desirable features of the existing "2 + 2" (dipyrromethane + dipyrromethane-1,9-dicarbinol) method, such as absence of scrambling, yet has significant advantages. The advantages include the absence of acid in the porphyrin-forming step, the use of a metal template for cyclization, the ability to carry out the reaction at high concentration, the lack of a quinone oxidant, avoidance of use of dichloromethane, and the increased yield of macrocycle formation to give the target ABCD-metalloporphyrin.}, number={20}, journal={JOURNAL OF ORGANIC CHEMISTRY}, author={Dogutan, Dilek Kiper and Zaidi, Syeda Huma H. and Thamyongkit, Patchanita and Lindsey, Jonathan S.}, year={2007}, month={Sep}, pages={7701–7714} }
 @article{kim_dogutan_ptaszek_lindsey_2007, title={Synthesis of hydrodipyrrins tailored for reactivity at the 1- and 9-positions}, volume={63}, ISSN={["0040-4020"]}, DOI={10.1016/j.tet.2006.10.027}, abstractNote={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 alpha-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.}, number={1}, journal={TETRAHEDRON}, author={Kim, Han-Je and Dogutan, Dilek Kiper and Ptaszek, Marcin and Lindsey, Jonathan S.}, year={2007}, month={Jan}, pages={37–55} }