Addition of organotellurium trihalides to acetylenes

Comasseto, J. V.; Stefani, Hélio A.; Chieffi, A.; Zukerman-Schpector, Júlio

doi:10.1021/om00050a010

Cited by 39 publications

(30 citation statements)

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“…Compounds 1-4 were prepared as previously described [52]. In a typical reaction, a solution of the 3-hydroxy alkyne (11 mmol) in dry benzene (10 mL) was added to a suspension of p-methoxyphenyltellurium trichloride/bromide (10 mmol) in dry benzene (40 mL).…”

Section: Experimental Synthesis and Crystal Growthmentioning

confidence: 99%

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Crystallographic and docking (Cathepsins B, K, L and S) studies on bioactive halotelluroxetanes

Caracelli

Maganhi

Cardoso

et al. 2017

Zeitschrift Für Kristallographie - Crystalline Materials

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Abstract. The molecular structures of the halotelluroxetanes pMeOC6H4Te(X)[C(=C(H)Xꞌ)C(CH2)nO], X = Xꞌ = Cl and n = 6 (1) and X = Cl, Xꞌ = Br and n = 5 (4), show similar binuclear aggregates sustained by { … Te-O}2 cores comprising covalent Te-O and secondary Te⋯O interactions. The resulting C2ClO2(lone-pair) sets define pseudo-octahedral geometries. In each structure, C-X⋯(arene) interactions lead to supramolecular layers. Literature studies have shown these and related compounds (i.e. 2: X = Xꞌ = Cl and n = 5; 3: X = Xꞌ = Br and n = 5) to inhibit Cathepsins B, K, L and S to varying extents. Molecular docking calculations have been conducted on ligands (i.e. cations derived by removal of the telluriumbound X atoms) 1ꞌ-3ꞌ (note 3ꞌ = 4ꞌ) enabling correlations between affinity for sub-sites and inhibition. The common feature of all docked complexes was the formation of a Te-S covalent bond with cysteine residues, the relative stability of the ligands with an E-configuration and the formation of a C-O … π interaction with the phenyl ring; for 1ꞌ the Te-S covalent bond was weak, a result correlating with its low inhibition profile. At the next level differences are apparent, especially with respect to the interactions formed by the organic-ligand-bound halides.

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Section: Experimental Synthesis and Crystal Growthmentioning

confidence: 99%

“…The resulting oils that were isolated after chromatography were recrystallised from CH2Cl2 for 1 and CHCl3/hexane for 2 and 4 to yield crystals suitable for X-ray analysis. The structure of 2 has already been described [52].…”

Section: Experimental Synthesis and Crystal Growthmentioning

confidence: 99%

Crystallographic and docking (Cathepsins B, K, L and S) studies on bioactive halotelluroxetanes

Caracelli

Maganhi

Cardoso

et al. 2017

Zeitschrift Für Kristallographie - Crystalline Materials

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“…Compound 1 was synthesised and characterised as per the literature procedure [15]. Crystals for the X-ray structure determination were obtained by slow evaporation of its chloroform/petroleum ether (1/1 v/v) solution.…”

Section: Experimental Synthesis and Crystal Growthmentioning

confidence: 99%

Crystallographic, DFT and docking (cathepsin B) studies on an organotellurium(IV) compound

Caracelli

Zukerman-Schpector

Madureira

et al. 2016

Zeitschrift Für Kristallographie - Crystalline Materials

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“…4 Reactions of organyltellurium trichlorides with alkynes also proceed as the syn addition resulting in Z organyl(2 chlorovinyl)tellurium dichlorides. 8, 9 The mechanism 8,9 including four membered cyclic transition state was suggested for the explanation of the stereospe cific syn addition of tellurium tetrachloride and organyl tellurium trichlorides to the triple bond. Reaction of tellurium tetrachloride with propargyl alcohol and its derivatives is a special case: substitution of the hydroxyl group for the chlorine atom at the tellurium atom result ing in formation of cyclic products occurs along with the addition to the triple bond.…”

Section: Reaction Of Tellurium Tetrachloride With Acetylenementioning

confidence: 99%

Reaction of tellurium tetrachloride with acetylene

et al. 2009

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No data on the reaction of tellurium tetrachloride with acetylene are available, however, it is known that tellurium tetrachloride reacts with substituted acetyl enes. 1-7 Reactions of tellurium tetrachloride with phenyl acetylene, diphenylacetylene, and arylalkynes are known to proceed as the syn addition resulting in Z configured products exclusively. 1-6 This was confirmed by X ray dif fraction data. 4 Reactions of organyltellurium trichlorides with alkynes also proceed as the syn addition resulting in Z organyl(2 chlorovinyl)tellurium dichlorides. 8,9 The mechanism 8,9 including four membered cyclic transition state was suggested for the explanation of the stereospe cific syn addition of tellurium tetrachloride and organyl tellurium trichlorides to the triple bond. Reaction of tellurium tetrachloride with propargyl alcohol and its derivatives is a special case: substitution of the hydroxyl group for the chlorine atom at the tellurium atom result ing in formation of cyclic products occurs along with the addition to the triple bond. 5 We carried out the addition of tellurium tetrachloride to acetylene for the first time (Scheme 1). It was estab lished that the reaction affords hitherto unknown E,E bis (2 chlorovinyl)tellurium dichloride (1) in 62% yield. The process proceeds in chloroform at 20-40 °С under acetyl ene pressure of ~12 atm. Scheme 1Dichloride 1 is a promising intermediate for the syn thesis of organotellurium products. This is a colorless crystalline substance, its structure was established by the 1 H and 13 C NMR spectroscopy and mass spectrometry and confirmed by data from elemental analysis. The spinspin coupling constant for trans vinyl protons of product 1 (J = 13.6 Hz) is typical of E 2 chlorovinyl chalco genides. 10,11 It is known 11 that the spin-spin coupling constants for cis vinyl protons of Z 2 chlorovinyl chalco genides are ~6.5 Hz. The mass spectrum of product 1 contains a peak of the ion with m/z 287, which corre sponds to the molecular ion of the product lacking one chlorine atom. It was established 12 that the mass spectra of diorganyltellurium dichlorides do not contain peaks of molecular ions, but there are the ions [M -Cl] + .Thus, the reaction of tellurium tetrachloride with acetylene (in contrast to other alkynes 1-7 ) proceeds as the anti addition and leads to the E configured product. The reaction is the first example of the stereospecific anti addition of tellurium tetrachloride to the triple bond of acetylenic hydrocarbons. One can suppose that, in the case of acetylene, the anti addition via three membered intermediates 2 and 3 (see Scheme 2) becomes more favorable than the syn addition.The formation of such a three membered intermedi ates is proposed in the reactions of organylsulfenyl and organylselenenyl chlorides with alkynes proceeding as the electrophilic anti addition. 13

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Addition of organotellurium trihalides to acetylenes

Cited by 39 publications

References 0 publications

Crystallographic and docking (Cathepsins B, K, L and S) studies on bioactive halotelluroxetanes

Crystallographic and docking (Cathepsins B, K, L and S) studies on bioactive halotelluroxetanes

Crystallographic, DFT and docking (cathepsin B) studies on an organotellurium(IV) compound

Reaction of tellurium tetrachloride with acetylene

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