Pd-catalyzed synthesis of C-C (Sonogashira, Suzuki, Heck, Stille), C-P and C-S linked products using gem -dibromovinyl BODIPY

2021 ◽  
pp. A-O
Author(s):  
Hasrat Ali ◽  
Brigitte Guérin ◽  
Johan E. van Lier
Keyword(s):  
Absorption Maximum ◽  
Palladium Catalysis ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
X Ray Diffraction ◽  
X Ray ◽  
H Nmr ◽  
Cross Coupling Reactions ◽  
Derivatives Of ◽  
C Nmr

The chemistry of gem-dibromovinyl derivatives has undergone a renaissance through the application of palladium catalysis and has been applied to pyrrole substituted gem-dibromovinyl BODIPY. gem-Dibromovinyl BODIPYs (substituted at either the [Formula: see text]-position of 8-phenyl or the [Formula: see text]-position of the pyrrole rings) were studied for cross-coupling reactions using Sonogashira, Suzuki, Heck and Stille conditions, and with phosphonates and thiols. The assigned structures were supported by MS and 1H NMR, [Formula: see text]C NMR, X-ray diffraction analysis as well as optical spectroscopy. The conjugates were investigated for their absorption, fluorescence and solvatochromic properties in different solvents. Substitution at the [Formula: see text]-position of 8-phenyl derivatives of gem-diethynyl BODIPYs did not induce any shift in the absorption maximum, while the [Formula: see text]-position pyrrole substituted derivatives showed a red shift. Aromatic compounds gave larger red shifts as compared to the aliphatic substituted analogs.

Synthesis and structural characterization of substituted phenols with a m-terphenyl backbone 2,4,6-R3C6H2OH (R=2,4,6-Me3C6H2, Me5C6)

2015 ◽  
Vol 70 (1) ◽  
pp. 77-81 ◽  
Author(s):  
Atena B. Şolea ◽  
Marian Olaru ◽  
Cristian Silvestru ◽  
Ciprian I. Raţ
Keyword(s):  
Grignard Reagent ◽  
Cross Coupling ◽  
Molecular Structures ◽  
Coupling Reactions ◽  
X Ray Diffraction ◽  
Substituted Phenols ◽  
X Ray ◽  
Cross Coupling Reactions ◽  
C Nmr

AbstractSubstituted phenols with a m-terphenyl backbone 2,4,6-R3C6H2OH [R=2,4,6-Me3C6H2 (1), Me5C6 (2)] were synthesized using Kumada cross-coupling reactions between 2,4,6-I3C6H2OH and the corresponding Grignard reagent. Both compounds were structurally characterized in solution by 1H and 13C NMR spectroscopy and HRMS. The molecular structures of 1 and 2 were determined by single-crystal X-ray diffraction.

β-Hydroxydithiozimtsäurederivate als Liganden. Synthese und Charakterisierung neuartiger 1,1-Ethendithiolato- und O,S-Chelatkomplexe / Derivatives of β -Hydroxydithiocinnamic Acids as Ligands. Syntheses and Characterisation of Novel 1,1-Ethenedithiolato and O,S-Chelate Complexes

2007 ◽  
Vol 62 (3) ◽  
pp. 475-482 ◽  
Author(s):  
Karsten Schubert ◽  
Helmar Görls ◽  
Wolfgang Weigand
Keyword(s):  
Bidentate Ligand ◽  
Molecular Structures ◽  
X Ray Diffraction ◽  
Chelate Complexes ◽  
X Ray ◽  
H Nmr ◽  
Hexyl Ester ◽  
Elemental Analyses ◽  
Derivatives Of ◽  
C Nmr

Starting from 4-bromoacetophenone 1, the 4-bromo-β -hydroxydithiocinnamic acid 2 and the 4-bromo-β -hydroxydithiocinnamic acid hexyl ester 3 were prepared using carbon disulfide and potassium-tert-butylate as a base. Acting as a ligand, the acid gives 1,1-ethenedithiolato complexes with (Ph3P)2Pt(II) (4a), (Et3P)2Pt(II) (4b), dppePt(II) (4c), (Ph3P)2Pd(II) (4d), dppePd(II) (4e), and dppeNi(II) (4f). In contrast to the acid, the deprotonated ester 3 forms a monoanionic bidentate ligand. [O,S] Complexes of Pt(II) (5a), Pd(II) (5b) and Ni(II) (5c) were obtained. All complexes have been fully characterised using 1H NMR, 13C NMR and 31P NMR spectroscopy, mass spectrometry, infrared spectroscopy and elemental analyses. The molecular structures of the complexes 4b and 5a - 5c were determined by X-ray diffraction analyses.

Improved Access to 1,8-Dichloro-10-(ethynyl)anthracene: A Useful Building Block for (Semi-)rigid Organic Frameworks

Synthesis ◽  
2018 ◽  
Vol 50 (10) ◽  
pp. 2009-2018
Author(s):  
Jan-Hendrik Lamm ◽  
Philipp Niermeier ◽  
Leif Körte ◽  
Beate Neumann ◽  
Hans-Georg Stammler ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Building Block ◽  
High Resolution Mass Spectrometry ◽  
Cross Coupling ◽  
Easy Access ◽  
Coupling Reactions ◽  
X Ray Diffraction ◽  
X Ray ◽  
Cross Coupling Reactions ◽  
Resolution Mass

An easy access to 1,8-dichloro-10-(ethynyl)anthracene is reported, which is widely applicable for building up rigid linkers between two 1,8-dichloroanthracene units. For this, 1,8-dichloroanthren-10(9H)-one was reacted with ethynylmagnesium bromide in the presence of CeCl3; the yield was 65%. This building block was used as a substrate in (cross-)coupling reactions and some examples of linked 1,8-dichloroanthracen-10-yls (e.g., 1,8-bis[(1,8-dichloroanthracen-10-yl)-ethynyl]naphthalene or 1,2-bis[(1,8-dichloroanthracen-10-yl)ethynyl]-benzene) were synthesized in good to moderate yields. Linked 1,8-dichloroanthracen-10-yl derivatives were also synthesized by cross-coupling reactions using 10-bromo-1,8-dichloroanthracene and doubly ethynyl-substituted substrates. Linkers between the 1,8-dichloroanthracene units were: butadiynediyl, dimethylsilyldiethynyl, octa-1,7-diyne-1,8-diyl, propane-1,3-diylbis(dimethylsilyl)diethynyl, benzene-1,2-diethynyl, naphthalene-1,8-diyldiethynyl, and anthracene-1,8-diyldiethynyl. The new anthracene compounds were characterized by NMR spectroscopy, high-resolution mass spectrometry, and, in part, by X-ray diffraction experiments.

scholarly journals Synthesis and X-ray Diffraction Study of thiosemicarbazone Palladacycles with dppm

Proceedings ◽  
2021 ◽  
Vol 62 (1) ◽  
pp. 13
Author(s):  
Marcos Rúa-Sueiro ◽  
Paula Munin-Cruz ◽  
Francisco Reigosa ◽  
José M. Vila ◽  
Juan M. Ortigueira
Keyword(s):  
Nmr Spectroscopy ◽  
31P Nmr ◽  
Antimicrobial Agents ◽  
Cross Coupling ◽  
31P Nmr Spectroscopy ◽  
Coupling Reactions ◽  
X Ray Diffraction ◽  
X Ray ◽  
Cross Coupling Reactions ◽  
Platinum Salt

Cyclometallated compounds have been extensively studied, in particular those with palladium and platinum. This is because of their possible applications in medicinal chemistry, as anticancer or antimicrobial agents; in some cases, with similar results as cisplatin, carboplatin or oxaliplatin. What is also remarkable is their use as homogeneous catalysts, for example, in cross coupling reactions such as Suzuki–Miyaura or Mizoroki–Heck. Herein, we report the synthesis of different thiosemicarbazone ligands, which will be reacted with a palladium or platinum salt, to give the corresponding cyclometallated compounds; in addition, their reactivity with bis(diphenylphosphino)methane (dppm) will be studied. Characterization has been carried out by elemental analysis, IR spectroscopy, 1H and 31P NMR spectroscopy. Additionally, 1c has been studied by X-ray diffraction.

scholarly journals Double N-arylation reaction of polyhalogenated 4,4’-bipyridines. Expedious synthesis of functionalized 2,7-diazacarbazoles

2012 ◽  
Vol 8 ◽  
pp. 253-258 ◽  
Author(s):  
Mohamed Abboud ◽  
Emmanuel Aubert ◽  
Victor Mamane
Keyword(s):  
Cross Coupling ◽  
Catalyst System ◽  
Coupling Reactions ◽  
X Ray Diffraction ◽  
X Ray ◽  
Cross Coupling Reactions ◽  
Π Stacking ◽  
Phenyl Rings ◽  
One Step ◽  
Site Selective

Unusual 2,7-diazacarbazoles were prepared in one step from readily available tetra-halogenated 4,4’-bipyridines by using a double N-arylation reaction in the presence of the Pd–XPhos catalyst system. Moderate to good yields were obtained in this site-selective Buchwald–Hartwig double amination. The functionalization of these tricyclic derivatives was performed by using Pd-catalyzed cross-coupling reactions such as the Stille and Suzuki couplings. Two compounds were analyzed by X-ray diffraction and show π–π stacking involving the diazacarbazole moieties and the phenyl rings of functionalized groups.

scholarly journals Toward the synthesis of thiadiazole-based therapeutic agents: synthesis, spectroscopic study, X-ray analysis, and cross-coupling reactions of the key intermediate 3,5-diiodo-1,2,4-thiadiazole

2019 ◽  
Vol 46 (2) ◽  
pp. 1507-1519
Author(s):  
Mohammed Boulhaoua ◽  
Ana Torvisco ◽  
Tibor Pasinszki
Keyword(s):  
Solid Phase ◽  
Cross Coupling ◽  
Therapeutic Agents ◽  
Biologically Active ◽  
Coupling Reactions ◽  
X Ray Diffraction ◽  
Reaction Conditions ◽  
X Ray ◽  
Cross Coupling Reactions ◽  
First Time

AbstractThe 1,2,4-thiadiazole moiety is an important component of several biologically active compounds, and varying substituents on this aromatic ring is one of the possible methods to develop novel thiadiazole-based drugs for medicine. A key building block to this end, namely 3,5-diiodo-1,2,4-thiadiazole (1), has been synthesized and characterized in this work for the first time. 1 has exhibited high selectivity for the replacement of iodine atom at position C5 (carbon next to sulfur) in Sonogashira-type cross-coupling reactions with phenylacetylene. Therefore, 3-iodo-5-(phenylethynyl)-1,2,4-thiadiazole (4) or 3,5-bis(phenylethynyl)-1,2,4-thiadiazole (5) could be synthesized selectively depending on reaction conditions. All three novel molecules have been characterized by NMR, IR, Raman, mass, and UV spectroscopies, and their solid phase structures have been determined by single-crystal X-ray diffraction. 1 is expected to be a key starting material for producing thiadiazole-based therapeutic agents using cross-coupling reactions.

Functionalized Pyrazoles as Agents in C–C Cross-Coupling Reactions

2014 ◽  
Vol 69 (1) ◽  
pp. 83-97 ◽  
Author(s):  
Marijana Pejic ◽  
Sebastian Popp ◽  
Michael Bolte ◽  
Matthias Wagner ◽  
Hans-Wolfram Lerner
Keyword(s):  
Cross Coupling ◽  
Boronic Acids ◽  
Aryl Halides ◽  
Second Step ◽  
Coupling Reactions ◽  
X Ray Diffraction ◽  
X Ray ◽  
Suzuki Reactions ◽  
Microwave Assisted ◽  
Cross Coupling Reactions

The 1-tetrahydropyranyl-(THP-)protected pyrazoles 4-R-pz(THP) (R=pinacolatoboryl=Bpin (3a(THP)), Me3Si (4a(THP)), Me3Sn (5a(THP)), and 4-R-3,5-Ph2pz (R=Bpin (3b(THP)), Me3Si (4b(THP)), Me3Sn (5b(THP)) were obtained by the following syntheses: i) In a first step, 4-X-pz (X=Br (1a), I (2a)) and 4-X-3,5-Ph2pz (X=Br (1b), I (2b)) were reacted with 3,4-dihydro-2Hpyran (DHP) to give the related THP-protected bromo- or iodopyrazole derivatives. ii) In a second step these THP derivatives were metalated by treatment with nBuLi or iPrMgCl. Subsequent reactions of the THP-protected metallopyrazoles 4-M-pz(THP) and 4-M-3,5-Ph2pz(THP) (M=Li, MgBr) with Bpin(OiPr), Me3SiCl, and Me3SnCl yielded the pyrazole derivatives 3a(THP), 3b(THP), 4a(THP), 4b(THP), 5a(THP), and 5b(THP). In contrast to the stannylated pyrazoles 5a(THP) and 5b(THP), the corresponding borylated and silylated derivatives could be easily deprotected: treatment of 3a(THP), 3b(THP), and 4a(THP) with HCl yielded the parent pyrazoles 3a, 3b and 4a. The microwave-assisted C-C cross-coupling reactions of these pyrazoles with aryl halides were examined, e. g. Suzuki reactions of 3a with p-pentylphenylbromide, p-hexylphenylbromide, and p- (2-ethylhexyl)phenylbromide. Similar reactions were also performed with 1a, 1b, 2a, and 2b and aryl-substituted pinacolatoboranes or boronic acids. Crystals of 5b(THP) suitable for X-ray diffraction were grown (monoclinic P21/c) and their structure determined. The crystal structures of 1a·HBr (monoclinic P21/n), 1b (triclinic P̄1̄), (1c)2·HBr (monoclinic P2/c), 1c·HBr·(Br2)0.5 (triclinic P̄1̄), (2a)3·H2SO4 (triclinic P̄1̄), 3a (orthorhombic P212121), (3a)3·H2O (trigonal R3c), 3b (orthorhombic Pna21), and 4a (monoclinic Pc) reveal interesting hydrogen bonding networks.

Comparison of the Suzuki cross-coupling reactions of 4,7-dichloroquinoline and 7-chloro-4-iodoquinoline with arylboronic acids using phosphine-free palladium catalysis in water

2004 ◽  
Vol 82 (2) ◽  
pp. 206-214 ◽  
Author(s):  
Richard W Friesen ◽  
Laird A Trimble
Keyword(s):  
Phenylboronic Acid ◽  
Palladium Catalysis ◽  
Suzuki Reaction ◽  
Tetrabutylammonium Bromide ◽  
Cross Coupling ◽  
Palladium Acetate ◽  
Coupling Reactions ◽  
Reaction Conditions ◽  
Arylboronic Acids ◽  
Cross Coupling Reactions

4,7-Dichloroquinoline (1a) and 7-chloro-4-iodoquinoline (1b) undergo Suzuki cross-coupling reactions with arylboronic acids catalyzed by phosphine-free palladium acetate in boiling water. Using phenylboronic acid (2), the reaction of 1a provides 7-chloro-4-phenylquinoline (3) (78%) together with diphenylquinoline (4) (12%), while 1b reacts in a much more regioselective fashion and provides 3 in 98% isolated yield. Although 1b undergoes a more regioselective Suzuki reaction than 1a, additional important observations are that the overall reaction of 1b with 2 is three times slower than 1a and that the reaction occurs in the absence of tetrabutylammonium bromide. Using optimized reaction conditions, a variety of aryl and vinylboronic acids undergo regioselective Suzuki cross-coupling with 1b to provide the products 7, 10, and 11 in good to excellent yield.Key words: palladium, cross-coupling, regioselectivity, quinolines, boronic acids.

scholarly journals Preparation of pyridine-3,4-diols, their crystal packing and their use as precursors for palladium-catalyzed cross-coupling reactions

2010 ◽  
Vol 6 ◽  
Author(s):  
Tilman Lechel ◽  
Irene Brüdgam ◽  
Hans-Ulrich Reissig
Keyword(s):  
Crystal Structure ◽  
Crystal Packing ◽  
Cross Coupling ◽  
Crystal Structure Analysis ◽  
Coupling Reactions ◽  
X Ray ◽  
Cross Coupling Reactions ◽  
Fluorescence Measurements ◽  
Subsequent Conversion ◽  
Palladium Catalyzed

A series of trifluoromethyl-substituted 3-alkoxypyridinol derivatives has been deprotected to furnish pyridine-3,4-diol derivatives in good yields. The X-ray crystal structure analysis proved that a 1:1 mixture of pyridine-3,4-diols and their pyridin-4-one tautomers exist in the solid state. Subsequent conversion into bis(perfluoroalkanesulfonate)s were smoothly achieved. The obtained compounds were used as substrates for palladium-catalyzed coupling reactions. Fluorescence measurements of the biscoupled products showed a maximum of emission in the violet region of the spectrum.

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