Acetylene-Triggered Reductive Incorporation of Phosphine Chalcogenides into a Quinoline Scaffold: Toward SNHAr Reaction

2019 ◽  
Vol 84 (10) ◽  
pp. 6244-6257 ◽  
Author(s):  
Boris A. Trofimov ◽  
Pavel A. Volkov ◽  
Kseniya O. Khrapova ◽  
Anton A. Telezhkin ◽  
Nina I. Ivanova ◽  
...  
Keyword(s):  
Phosphine Chalcogenides

Solution multinuclear (31P,111Cd,77Se) magnetic resonance studies of cadmium complexes of heterocyclic aromatic thiones and the structure of [tetrakis(2(1H)-pyridinethione)cadmium] nitrate, [Cd(C5H5NS)4](NO3)2

2000 ◽  
Vol 78 (5) ◽  
pp. 590-597 ◽  
Author(s):  
Umarani Rajalingam ◽  
Philip AW Dean ◽  
Hilary A Jenkins
Keyword(s):  
Cadmium Nitrate ◽  
Cadmium Complexes ◽  
Nmr Studies ◽  
X Ray ◽  
X Ray Crystallography ◽  
Stoichiometric Reaction ◽  
Complex Salts ◽  
Reduced Temperature ◽  
Aromatic Heterocyclic ◽  
Phosphine Chalcogenides

The complex salts CdL4(O3SCF3)2 (L = 2(1H)-pyridinethione (Py2SH), 4(1H)-pyridinethione (Py4SH), or 2(1H)-quinolinethione (Q2SH)) have been synthesized by the stoichiometric reaction of Cd(O3SCF3)2 and the appropriate thione. Both ambient-temperature 13C and reduced-temperature 111Cd NMR of CdL4(O3SCF3)2 in solution are consistent with L being bound through sulfur. Reduced-temperature NMR (31P, 77Se, 111Cd, as appropriate) of mixtures of CdL4(O3SCF3)2 and Cd(EPCy3)4(O3SCF3)2 (E = Se, Cy = c-C6H11) and of Cd(EPCy3)4(O3SCF3)2 (E = S, Se) and L in solution provides evidence for various [CdLn(EPCy3)4-n]2+. Similarly, reduced-temperature metal NMR of [CdL4]2+ and [CdL'4]2+ (L, L' = Py2SH, Py4SH, Q2SH; L not equal L') in solution shows the formation of [CdLnL'4-n]2+. Thus it has been demonstrated that at reduced temperature [CdL4]2+ is intact in solution and exchange of L is slow on the timescale of the metal chemical shift differences. From the NMR studies of Cd(EPCy3)4(O3SCF3)2 (E = S, Se):L mixtures, the binding preferences are found to be L > EPCy3 in solution. Similarly, from the reduced temperature metal NMR spectra of mixtures where L and L' compete for Cd(II) in solution, the binding preferences are Py4SH > Py2SH > Q2SH. The structure of Cd(Py2SH)4(NO3)2 (4) has been determined by single crystal X-ray analysis. Colorless crystals of 4 are tetragonal, I4(1)/acd with 8 molecules per unit cell of dimensions a = 18.660(3), c = 15.215(3) Å. The structure is comprised of recognizable NO3- anions and [Cd(Py2SH)4]2+ cations. In the cations, which have S4 symmetry, the ligands are S-bound. A network of NH···O hydrogen bonds links the cations and anions.Key words: aromatic heterocyclic thiones, cadmium complexes, phosphine chalcogenides, 111Cd, 31P, 77Se NMR, X-ray crystallography.

The use of phosphine chalcogenides in the preparation of cobalt chalcogenides

1993 ◽  
Vol 449 (1-2) ◽  
pp. 167-172 ◽  
Author(s):  
S.M. Stuczynski ◽  
Y.-U. Kwon ◽  
M.L. Steigerwald
Keyword(s):  
Phosphine Chalcogenides

An Expedient Access to γ-Ketophosphine Chalcogenides via the Chemo- and Regioselective Addition of Secondary Phosphine Chalcogenides to β,γ-Ethylenic Ketones

2015 ◽  
Vol 26 (6) ◽  
pp. 455-462 ◽  
Author(s):  
Alexander V. Artem'ev ◽  
Svetlana F. Malysheva ◽  
Nataliya A. Belogorlova ◽  
Nadezhda I. Protzuk ◽  
Alexander I. Albanov ◽  
...  
Keyword(s):  
Secondary Phosphine ◽  
Secondary Phosphine Chalcogenides ◽  
Regioselective Addition ◽  
Phosphine Chalcogenides

ChemInform Abstract: Phosphine Chalcogenides

ChemInform ◽  
2012 ◽  
Vol 43 (8) ◽  
pp. no-no
Author(s):  
G. Keglevich
Keyword(s):  
Phosphine Chalcogenides

ChemInform Abstract: Phosphine Chalcogenides

ChemInform ◽  
2013 ◽  
Vol 44 (12) ◽  
pp. no-no
Author(s):  
G. Keglevich
Keyword(s):  
Phosphine Chalcogenides

One-pot reductive N-vinylation and C(4)-phosphorylation of pyridines with alkyl propiolates and secondary phosphine chalcogenides

2015 ◽  
Vol 56 (33) ◽  
pp. 4804-4806 ◽  
Author(s):  
Nina K. Gusarova ◽  
Pavel A. Volkov ◽  
Nina I. Ivanova ◽  
Svetlana N. Arbuzova ◽  
Kseniya O. Khrapova ◽  
...  
Keyword(s):  
Secondary Phosphine ◽  
One Pot ◽  
Secondary Phosphine Chalcogenides ◽  
Alkyl Propiolates ◽  
Phosphine Chalcogenides

ChemInform Abstract: One-Pot Reductive N-Vinylation and C(4)-Phosphorylation of Pyridines with Alkylpropiolates and Secondary Phosphine Chalcogenides.

ChemInform ◽  
2015 ◽  
Vol 46 (47) ◽  
pp. no-no
Author(s):  
Nina K. Gusarova ◽  
Pavel A. Volkov ◽  
Nina I. Ivanova ◽  
Svetlana N. Arbuzova ◽  
Kseniya O. Khrapova ◽  
...  
Keyword(s):  
Secondary Phosphine ◽  
One Pot ◽  
Secondary Phosphine Chalcogenides ◽  
Phosphine Chalcogenides

scholarly journals Electron-Deficient Acetylenes as Three-Modal Adjuvants in SNH Reaction of Pyridinoids with Phosphorus Nucleophiles

Molecules ◽  
2021 ◽  
Vol 26 (22) ◽  
pp. 6824
Author(s):  
Boris A. Trofimov ◽  
Pavel A. Volkov ◽  
Anton A. Telezhkin
Keyword(s):  
Nucleophilic Addition ◽  
Pyridine Ring ◽  
Cross Coupling ◽  
Secondary Phosphine ◽  
Metal Free ◽  
Secondary Phosphine Chalcogenides ◽  
Heterocyclic Moiety ◽  
Acid Esters ◽  
Phosphine Chalcogenides

Publications covering a new easy metal-free functionalization of pyridinoids (pyridines, quinolines, isoquinolines, acridine) under the action of the system of electron-deficient acetylenes (acetylenecarboxylic acid esters, acylacetylenes)/P-nucleophiles (phosphine chalcogenides, H-phosphonates) are reviewed. Special attention is focused on a SNH reaction of the regioselective cross-coupling of pyridines with secondary phosphine chalcogenides triggered by acylacetylenes to give 4-chalcogenophosphorylpyridines. In these processes, acetylenes act as three-modal adjuvants (i) activating the pyridine ring towards P-nucleophiles, (ii) deprotonating the P-H bond and (iii) facilitating the nucleophilic addition of the P-centered anion to a heterocyclic moiety followed by the release of the selectively reduced acetylenes (E-alkenes).

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