uu.seUppsala University Publications
Change search
Link to record
Permanent link

Direct link
BETA
Arkhypchuk, Anna I.
Alternative names
Publications (10 of 20) Show all publications
Xiong, R., Arkhypchuk, A. I. & Borbas, K. E. (2019). Attempted syntheses of N-confused hydroporphyrins through modified Lindsey routes. Journal of Porphyrins and Phthalocyanines, 23(4-5), 589-598
Open this publication in new window or tab >>Attempted syntheses of N-confused hydroporphyrins through modified Lindsey routes
2019 (English)In: Journal of Porphyrins and Phthalocyanines, ISSN 1088-4246, E-ISSN 1099-1409, Vol. 23, no 4-5, p. 589-598Article in journal (Refereed) Published
Abstract [en]

Unlike N-confused porphyrins which are well-known and extensively studied tetrapyrroles, N-confused hydroporphyrins are almost unknown, largely because so far they have resisted attempts at rational synthesis. Here, we report our efforts towards the total synthesis of N-confused hydroporphyrins. We have prepared N-confused building blocks analogous to the non-N-confused substrates in the Lindsey synthesis of sparsely substituted chlorins. We have systematically flipped the A, B and C pyrrole rings in the dipyrrolic precursors of the target N-confused macrocycles, preparing in total an N-confused "Western half' (tetrahydrodipyrrin) and two N-confused "Eastern halves" (brominated formyldipyrromethanes). These were subjected to a range of cyclization conditions. While we successfully isolated and identified three macrocyclic products, none of these proved to be the desired N-confused hydroporphyrin.

Place, publisher, year, edition, pages
WORLD SCI PUBL CO INC, 2019
Keywords
hydroporphyrins, N-confused tetrapyrroles, chlorins, 2+2 condensation, corrins
National Category
Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-387228 (URN)10.1142/S1088424619500524 (DOI)000468181100026 ()
Funder
Swedish Research CouncilStiftelsen Olle Engkvist Byggmästare
Available from: 2019-06-20 Created: 2019-06-20 Last updated: 2019-06-20Bibliographically approved
Obermeier, M. & Arkhypchuk, A. I. (2019). Phospholones from Diacetylenic Ketones: Synthesis, Properties, and Reactivity. Journal of Organic Chemistry, 84(6), 3491-3499
Open this publication in new window or tab >>Phospholones from Diacetylenic Ketones: Synthesis, Properties, and Reactivity
2019 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 84, no 6, p. 3491-3499Article in journal (Refereed) Published
Abstract [en]

The reactivity of phosphanyl phosphonates toward diacetylenic ketones was studied. Reactions resulted in the selective formation of phospholones via phosphaalkene intermediates. Phospholones were obtained in yields of 37-96% depending on the substituent on the acetylenic unit. Reduction of the phenyl-substituted phospholone resulted in the formation of a persubstituted phosphole bearing a hydroxyl group in position 3 in 64% yield, and its oxidation led to oxaphospholone in 77% yield. Both of these modifications led to substantial changes in the optoelectronic properties of the compounds and bathochromic shifts of the longest wavelength absorption maximum.

National Category
Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-381078 (URN)10.1021/acs.joc.9b00076 (DOI)000461844000039 ()30788966 (PubMedID)
Available from: 2019-04-23 Created: 2019-04-23 Last updated: 2019-04-23Bibliographically approved
D'Imperio, N. & Arkhypchuk, A. I. (2019). Reactivity patterns of benzhydryl(mesityl)phosphane oxide: a potential intermediate in carbonyl-carbonyl coupling reactions?. Paper presented at 22nd International Conference on Phosphorus Chemistry (ICPC), JUL 08-13, 2018, Budapest, HUNGARY. Phosphorus Sulfur and Silicon and the Related Elements, 194(4-6), 575-579
Open this publication in new window or tab >>Reactivity patterns of benzhydryl(mesityl)phosphane oxide: a potential intermediate in carbonyl-carbonyl coupling reactions?
2019 (English)In: Phosphorus Sulfur and Silicon and the Related Elements, ISSN 1042-6507, E-ISSN 1563-5325, Vol. 194, no 4-6, p. 575-579Article in journal (Refereed) Published
Abstract [en]

Benzhydryl(mesityl)phosphane oxide 2-H is prepared and its deprotonation and nucleophilicity behavior investigated. Treatment of lithium salts of 2-H with MeI results in methylation at the P-center while the benzyl carbon is not affected. Only upon double lithiation, it is possible to methylate also the benzyl carbon. Di-anion 2-2Li is reactive towards benzaldehyde to afford moderate amounts of triphenylethene after basic work.

Keywords
Aldehyde-aldehyde coupling, alkenes, nucleophilicity, reactivity study
National Category
Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-392062 (URN)10.1080/10426507.2018.1543305 (DOI)000473545900091 ()
Conference
22nd International Conference on Phosphorus Chemistry (ICPC), JUL 08-13, 2018, Budapest, HUNGARY
Funder
Swedish Research Council
Available from: 2019-09-10 Created: 2019-09-10 Last updated: 2019-09-10Bibliographically approved
Arkhypchuk, A. I., D'Imperio, N. & Ott, S. (2019). Triarylalkenes from the site-selective reductive cross-coupling of benzophenones and aldehydes. Chemical Communications, 55(43), 6030-6033
Open this publication in new window or tab >>Triarylalkenes from the site-selective reductive cross-coupling of benzophenones and aldehydes
2019 (English)In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, Vol. 55, no 43, p. 6030-6033Article in journal (Refereed) Published
Abstract [en]

PhP(Li)TMS converts benzophenones to phosphaalkenes which upon activation under oxidizing, basic conditions react with aromatic aldehydes under the formation of triarylalkenes. The one-pot reaction omits transition metals, proceeds at room temperature and precludes the formation of any homo-coupling products. Systematic substrate variations reveal reactivity patterns that are useful for the identification of ketone/aldehyde combinations that can be coupled in yields up to 80%.

National Category
Physical Chemistry Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-387587 (URN)10.1039/c9cc02972a (DOI)000468832200007 ()31062780 (PubMedID)
Available from: 2019-06-26 Created: 2019-06-26 Last updated: 2019-06-26Bibliographically approved
D'Imperio, N., Arkhypchuk, A. I., Mai, J. & Ott, S. (2019). Triphenylphosphaalkenes in Chemical Equilibria. European Journal of Inorganic Chemistry (11-12), 1562-1566
Open this publication in new window or tab >>Triphenylphosphaalkenes in Chemical Equilibria
2019 (English)In: European Journal of Inorganic Chemistry, ISSN 1434-1948, E-ISSN 1099-1948, no 11-12, p. 1562-1566Article in journal (Refereed) Published
Abstract [en]

Triphenylphosphaalkenes 1a-c were prepared in good to excellent yields in a modified phospha-Peterson reaction between PhP(Li)TMS and benzophenones with different para-substituents at the C-phenyl groups (a: R = H, b: R = O-octyl, c: R = F). Owing to the low kinetic stabilization that is provided by the P-phenyl group, compounds 1a-c engage in reversible dimerization and oligomerization reactions, some of which are not detectable by 31P NMR monitoring. The dimers and oligomers are in chemical equilibria with monomeric 1a-c, and can be converted quantitatively to phosphinites 4a-c by the irreversible addition of methanol across the P=C double bond.

National Category
Inorganic Chemistry
Research subject
Chemistry
Identifiers
urn:nbn:se:uu:diva-368871 (URN)10.1002/ejic.201801322 (DOI)000462351000016 ()
Funder
Swedish Research Council
Available from: 2018-12-09 Created: 2018-12-09 Last updated: 2019-04-12Bibliographically approved
Arkhypchuk, A. I., Orthaber, A., Kovacs, D. & Borbas, K. E. (2018). Isolation and Characterization of a Monoprotonated Hydroporphyrin. European Journal of Organic Chemistry (48), 7051-7056
Open this publication in new window or tab >>Isolation and Characterization of a Monoprotonated Hydroporphyrin
2018 (English)In: European Journal of Organic Chemistry, ISSN 1434-193X, E-ISSN 1099-0690, no 48, p. 7051-7056Article in journal (Refereed) Published
Abstract [en]

A simple protocol for the controlled preparation of mono- and diprotonated hydroporphyrins (chlorins) is presented. The chlorins carried 10-aryl groups with electron-neutral (phenyl), electron-donating (p-OMe-C6H4) or electron-withdrawing (pentafluorophenyl) substituents. The protonation reactions were readily followed by UV/Vis absorption spectroscopy, enabling the determination of the first (4.8-5.3) and second pK(a)'s (1.7-0.5). Both mono- and diprotonated species were fully characterized by H-1 NMR spectroscopy, which, in combination with theoretical studies, showed that these macrocycles were significantly distorted in solution. A 10-phenyl-substituted monoprotonated chlorin was characterized by X-ray crystallography. This is the first structurally characterized hydroporphyrin monocation, and the first crystal structure of a sterically unencumbered singly protonated tetrapyrrole. The photostabilities of the mono- and diprotonated 10-phenylchlorins were measured upon irradiation into their Soret bands; protonation yielded increased photostabilities.

Keywords
Functional organic materials, Chlorin, Tetrapyrrole, Protonation, Absorption, Fluorescence
National Category
Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-374119 (URN)10.1002/ejoc.201801472 (DOI)000454532300027 ()
Funder
Swedish Research Council, 2013-4655Stiftelsen Olle Engkvist Byggmästare
Available from: 2019-01-23 Created: 2019-01-23 Last updated: 2019-01-23Bibliographically approved
Arkhypchuk, A. I., D'Imperio, N. & Ott, S. (2018). One-Pot Intermolecular Reductive Cross-Coupling of Deactivated Aldehydes to Unsymmetrically 1,2-Disubstituted Alkenes. Organic Letters, 20(17), 5086-5089
Open this publication in new window or tab >>One-Pot Intermolecular Reductive Cross-Coupling of Deactivated Aldehydes to Unsymmetrically 1,2-Disubstituted Alkenes
2018 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 20, no 17, p. 5086-5089Article in journal (Refereed) Published
Abstract [en]

The phospha-Peterson reaction between a lithiated secondary phosphane, MesP(Li)TMS, and an aldehyde affords Mes-phosphaalkenes which, upon methanol addition and P-oxidation, react with a second carbonyl compound site specifically to produce unsymmetric alkenes. The E/Z selectivity of the one-pot cross coupling is largely determined by the electronic nature of the aryl substituent of the first aldehyde, with electron-donating groups giving rise to increased amounts of Z-alkenes.

National Category
Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-366262 (URN)10.1021/acs.orglett.8b01754 (DOI)000444527000003 ()30102547 (PubMedID)
Funder
Swedish Research Council
Available from: 2018-11-19 Created: 2018-11-19 Last updated: 2018-11-19Bibliographically approved
Mai, J., Arkhypchuk, A. I., Gupta, A. K. & Ott, S. (2018). Reductive coupling of two aldehydes to unsymmetrical E-alkenes via phosphaalkene and phosphinate intermediates. Chemical Communications, 54(52), 7163-7166
Open this publication in new window or tab >>Reductive coupling of two aldehydes to unsymmetrical E-alkenes via phosphaalkene and phosphinate intermediates
2018 (English)In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, Vol. 54, no 52, p. 7163-7166Article in journal (Refereed) Published
Abstract [en]

Stilbenes with push-pull electronics are directly accessible from an electron-rich and an electron-deficient benzaldehyde in a novel reductive aldehyde cross-coupling reaction. The one-pot procedure is enabled by the oxidation of a transient phosphinite to the corresponding phosphinate which exhibits sufficient reactivity towards deactivated aldehydes.

National Category
Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-362015 (URN)10.1039/c8cc04218g (DOI)000436290100012 ()29888363 (PubMedID)
Funder
Swedish Research Council
Available from: 2018-10-05 Created: 2018-10-05 Last updated: 2018-12-09Bibliographically approved
Xiong, R., Bornhof, A.-B., Arkhypchuk, A., Orthaber, A. & Borbas, E. (2017). Furan- and Thiophene-Based Auxochromes Red-shift Chlorin Absorptions and Enable Oxidative Chlorin Polymerizations. Chemistry - A European Journal, 23(17), 4089-4095
Open this publication in new window or tab >>Furan- and Thiophene-Based Auxochromes Red-shift Chlorin Absorptions and Enable Oxidative Chlorin Polymerizations
Show others...
2017 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 23, no 17, p. 4089-4095Article in journal (Refereed) Published
Abstract [en]

The de novo syntheses of chemically stable chlorins with five-membered heterocyclic (furane, thiophene, formylfurane and formylthiophene) substituents in selected meso- and beta-positions are reported. Heterocycle incorporation in the 3- and 13-positions shifted the chlorin absorption and emission to the red (up to lambdaem =680 nm), thus these readily incorporated substituents function analogously to auxochromes present in chlorophylls, for example, formyl and vinyl groups. Photophysical, theoretical and X-ray crystallographic experiments revealed small but significant differences between the behavior of the furan- and the thiophene-based auxochromes. Four regioisomeric bis-thienylchlorins (3,10; 3,13, 3,15 and 10,15) were oxidatively electropolymerized; the chlorin monomer geometry had a profound impact on the polymerization efficiency and the electrochemical properties of the resulting material. Chemical co-polymerization of 3,13-bis-thienylchlorin with 3-hexylthiophene yielded an organic-soluble red-emitting polymer.

Keywords
chlorins, electrochemistry, photophysics, polymerization, porphyrinoids
National Category
Organic Chemistry
Research subject
Chemistry with specialization in Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-317978 (URN)10.1002/chem.201604655 (DOI)000399312700011 ()27859811 (PubMedID)
Funder
Stiftelsen Olle Engkvist ByggmästareSwedish Research Council, 2013-4655Swedish Research Council, 2013-4763
Available from: 2017-03-22 Created: 2017-03-22 Last updated: 2017-12-28Bibliographically approved
Arkhypchuk, A. I., Orthaber, A. & Borbas, K. E. (2017). Synthesis and Characterization of Ferrocenyl Chlorins, 1,1'-Ferrocene-Linked Chlorin Dimers, and their BODIPY Analogues. Inorganic Chemistry, 56(5), 3044-3054
Open this publication in new window or tab >>Synthesis and Characterization of Ferrocenyl Chlorins, 1,1'-Ferrocene-Linked Chlorin Dimers, and their BODIPY Analogues
2017 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 56, no 5, p. 3044-3054Article in journal (Refereed) Published
Abstract [en]

We present the synthesis and characterization of meso-ferrocenyl-substituted hydroporphyrins (chlorins) and 1,1' -linked chlorin dimers. The dipyrromethane chlorin precursors were also transformed into Fc-substituted BODIPYs and 1,1'-ferrocenyl-linked BODIPY dimers. The chlorin dimers were studied by 1D and 2D NMR experiments and DFT calculations, which showed that their solution structures were dependent on the central metal. Monomeric and dimeric Ni(II) chlorins had similar H-1 NMR spectra. Monomeric and dimeric free base, Zn(II), and Pd(II) chlorins, on the other hand, showed significantly more different spectra. The eclipsed conformer of the free base chlorin dimer was calculated to be energetically more favored than the open form. The chlorin and BODIPY fluorescence emissions were quenched in the Fcsubstituted compounds; these could be recovered by oxidation of the Fe(II) center. Cyclic voltammetry showed up to five oxidation waves for the free base chlorin dimer, which suggests that the macrocycles were not behaving independently of each other.

National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-320661 (URN)10.1021/acs.inorgchem.6b03158 (DOI)000395847300076 ()28186734 (PubMedID)
Funder
Swedish Research Council, 2013-4655Stiftelsen Olle Engkvist Byggmästare
Available from: 2017-06-30 Created: 2017-06-30 Last updated: 2017-06-30Bibliographically approved
Organisations

Search in DiVA

Show all publications