10002-30-9Relevant articles and documents
S-(2-pyridinyl)-1,1,3,3-tetramethylthiouronium hexafluorophosphate. A new reagent for the synthesis of 2-pyridinethiol esters
Scardovi, Noemi,Garner, Philip P.,Protasiewicz, John D.
, p. 1633 - 1635 (2003)
(Matrix presented) A new thiouronium-based reagent for the synthesis of 2-pyridinethiol esters under non-nucleophilic conditions from the corresponding carboxylic acids was developed. The resulting procedure enables the preparation of previously unavailable α,β-unsaturated 2-pyridinethiol esters as well as their aliphatic and aromatic counterparts.
Cobalt-catalyzed acylation-reactions of (hetero)arylzinc pivalates with thiopyridyl ester derivatives
Lutter, Ferdinand H.,Grokenberger, Lucie,Hofmayer, Maximilian S.,Knochel, Paul
, p. 8241 - 8245 (2019/09/19)
A cobalt-catalyzed acylation reaction of various primary, secondary and tertiary alkyl, benzyl and (hetero)aryl S-pyridyl thioesters with (hetero)arylzinc pivalates is reported. The thioesters were prepared directly from the corresponding carboxylic acids under mild conditions, thus tolerating sensitive functional groups. Acylations of α-chiral S-pyridyl esters proceeded with very high stereoretention leading to optically enriched α-chiral ketones.
Ketones from Nickel-Catalyzed Decarboxylative, Non-Symmetric Cross-Electrophile Coupling of Carboxylic Acid Esters
Wang, Jiang,Cary, Brian P.,Beyer, Peyton D.,Gellman, Samuel H.,Weix, Daniel J.
supporting information, p. 12081 - 12085 (2019/08/12)
Synthesis of the C?C bonds of ketones relies upon one high-availability reagent (carboxylic acids) and one low-availability reagent (organometallic reagents or alkyl iodides). We demonstrate here a ketone synthesis that couples two different carboxylic acid esters, N-hydroxyphthalimide esters and S-2-pyridyl thioesters, to form aryl alkyl and dialkyl ketones in high yields. The keys to this approach are the use of a nickel catalyst with an electron-poor bipyridine or terpyridine ligand, a THF/DMA mixed solvent system, and ZnCl2 to enhance the reactivity of the NHP ester. The resulting reaction can be used to form ketones that have previously been difficult to access, such as hindered tertiary/tertiary ketones with strained rings and ketones with α-heteroatoms. The conditions can be employed in the coupling of complex fragments, including a 20-mer peptide fragment analog of Exendin(9–39) on solid support.
An Improved N-Acylation of 1 H-Benzotriazole Using 2,2′-Dipyridyl?-di?-sulfide and Triphenylphosphine
Singh, Anoop S.,Agrahari, Anand K.,Mishra, Nidhi,Singh, Mala,Tiwari, Vinod K.
, p. 470 - 476 (2019/01/10)
A novel path has been developed for the conversion of carboxylic acids into the corresponding N-acylbenzotriazoles by using 2,2′-dipyridyl disulfide/PPh 3 in anhydrous dichloromethane in the presence of 1 H-benzotriazole. Mild reaction conditio
Photoinduced Dynamics of Bis-dipyrrinato-palladium(II) and Porphodimethenato-palladium(II) Complexes: Governing Near Infrared Phosphorescence by Structural Restriction
Riese, Stefan,Holzapfel, Marco,Schmiedel, Alexander,Gert, Ingo,Schmidt, David,Würthner, Frank,Lambert, Christoph
supporting information, p. 12480 - 12488 (2018/10/25)
Although superficially similar, the bis-dipyrrinato-palladium(II) complex 1 and the bridged porphodimethenato-palladium(II) complex 2 possess dramatically different structures in the ground state (proved by X-ray structure analysis) and in the singlet and
Two-photon oxygen sensing with quantum dot-porphyrin conjugates
Lemon, Christopher M.,Karnas, Elizabeth,Bawendi, Moungi G.,Nocera, Daniel G.
supporting information, p. 10394 - 10406 (2013/10/01)
Supramolecular assemblies of a quantum dot (QD) associated to palladium(II) porphyrins have been developed to detect oxygen (pO2) in organic solvents. Palladium porphyrins are sensitive in the 0-160 Torr range, making them ideal phosphors for i
Synthesis of urea picket porphyrins and their use in the elucidation of the role buried solvent plays in the selectivity and stoichiometry of anion binding receptors
Calderon-Kawasaki, Kenichi,Kularatne, Sumith,Yue, Hu Li,Noll, Bruce C.,Scheidt, W. Robert,Burns, Dennis H.
, p. 9081 - 9087 (2008/04/05)
(Chemical Equation Presented) The synthesis of α,α-5,10-diurea and α,α,α-5,10,15-triurea picket porphyrins are detailed in this report. In previous reports, these porphyrins, along with α,α,α,α-5,10,15,20-tetraurea picket porphyrin, were used to demonstra
Metal complexation of 1-acyldipyrromethanes and porphyrins formed therefrom
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Page/Page column 7; 19, (2008/06/13)
A first aspect of the invention is a method of making a porphyrin-metal complex, comprising: (a) providing a first reagent selected from the group consisting of 1-acyldipyrromethanes, 1-acyldipyrrins, dipyrromethane-1-carbinols 1,9-diacyldipyrromethanes and 1,9-diacyldipyrrins; and then (b) condensing the first reagent with either itself (in the case of 1-acyldipyrromethanes, 1-acyldipyrrins, and dipyrromethane-1-carbinols) or a dipyrromethane (in the case of 1,9-diacyldipyrromethanes and 1,9-diacyldipyrrins) in a reaction mixture comprising a solvent and a second reagent selected from the group consisting of palladium and copper complexes to produce the porphyrin-metal complex (with the metal being palladium or copper). In preferred embodiments of the foregoing, the reaction mixture further comprises a base such as KOH or NaH.
Direct synthesis of palladium porphyrins from acyldipyrromethanes
Sharada, Duddu S.,Muresan, Ana Z.,Muthukumaran, Kannan,Lindsey, Jonathan S.
, p. 3500 - 3510 (2007/10/03)
(Chemical Equation Presented) Palladium porphyrins are valuable photosensitizers and luminescent agents in biology and materials chemistry. New methodology is described wherein a 1-acyldipyrromethane is converted into the palladium chelate of a trans-A2B2 porphyrin via a one-flask reaction. The reaction entails self-condensation of the 1-acyldipyrromethane in refluxing ethanol containing KOH (5-10 mol equiv) and Pd(CH3CN)2Cl2 (0.6 mol equiv) exposed to air. This direct route to palladium porphyrins is more expedient than the four steps of the traditional synthesis: (1) reduction of the 1-acyldipyrromethane; (2) acid-catalyzed condensation; (3) oxidation of the porphyrinogen intermediate; and (4) metal insertion. The new synthesis requires neither acid nor DDQ and formally entails only a 2e- + 2H+ oxidation overall versus the traditional multistep synthesis which requires a 2e- + 2H + reduction per each 1-acyldipyrromethane (4e- + 4H + overall) followed by a 6e- + 6H+ oxidation. The analogous reaction of a 1,9-diacyldipyrromethane and a dipyrromethane also gives the palladium porphyrin. Seven palladium porphyrins have been prepared in yields of 25-57%. The direct route also can be used with Cu(OAc) 2·H2O to give the copper porphyrin albeit in low yield. In summary, this methodology readily affords palladium porphyrins directly from acyldipyrromethanes.
Efficient synthesis of monoacyl dipyrromethanes and their use in the preparation of sterically unhindered trans-porphyrins
Rao, Polisetti Dharma,Littler, Benjamin J.,Geier III, G. Richard,Lindsey, Jonathan S.
, p. 1084 - 1092 (2007/10/03)
The condensation of an aldehyde with a dipyrromethane bearing a sterically unhindered aryl substituent at the 5-position typically results in low yield and a mixture of porphyrin products derived from acidolytic scrambling. We have developed a concise nonscrambling synthesis of such trans-porphyrins that takes advantage of the availability of multigram quantities of dipyrromethanes. This route involves the selective monoacylation of the dipyrromethanes with a pyridyl thioester, reduction of the monoacyl dipyrromethane to the corresponding carbinol, and self- condensation of the carbinol to form the porphyrin. The monoacylation procedure has wide scope as demonstrated by the preparation of a set of 15 diverse monoacyl dipyrromethanes in good yield at the multigram scale. The dipyrromethanecarbinol self-condensation reaction is extremely rapid (3 min) under mild room-temperature conditions and affords the trans-porphyrin in 16- 28% yield. Analysis by laser-desorption mass spectrometry (LD-MS) of samples from the crude reaction mixture revealed no scrambling within the limit of detection (1 part in 100). The self-condensation is compatible with a range of electron-withdrawing or -releasing substituents as well as substituents for building block applications (TMS-ethyne, ethyne, iodo, ester). The absence of any detectable scrambling in the self-condensation enables a simple purification. The synthesis readily affords gram quantities of pure, sterically unhindered trans-porphyrins in a process involving minimal chromatography.
