Structures of Copper Complexes of the Hybrid [SNS] Ligand of Bis(2-(benzylthio)ethyl)amine and Facile Catalytic Formation of 1-Benzyl-4-phenyl-1<i>H</i>-1,2,3-triazole through Click Reaction

Bai, Shi‐Qiang; Koh, Lip Lin; Hor, T. S. Andy

doi:10.1021/ic801690v

Cited by 76 publications

(31 citation statements)

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“…At low temperatures, the 1 H and 13 C NMR spectra of the complexes (1)(2)(3)(4)(5) indicate the presence of two invertomers a and b, of similar abundance. Each of them gives two sets of signals, in that the N,S-chelation makes non-equivalent the dithioether protons and carbons which are equivalent in the free ligands.…”

Section: Discussionmentioning

confidence: 98%

“…The coordination chemistry of hybrid ligands, especially those with labile or hemilabile functions to promote dynamic properties such as solution equilibria, fluxional processes and catalytic reversibility, is an active area of research [1][2][3][4][5][6]. Our recent NMR studies concerned the solution stereodynamics of ruthenium(II) complexes of a range of hybrid sulfur nitrogen ligands based on pyridine or pyrimidine [7][8][9][10][11].…”

Section: Introductionmentioning

confidence: 99%

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Fluxional rearrangement in congested ruthenium(II) complexes containing pyrimidine- and/or pyridine-based dithioether ligands

Tresoldí

Pietro

Drommi

et al. 2009

Transition Met Chem

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The solvento species obtained by the treatment of cis-RuCl 2 (N,N-L) 2 [L = di-2-pyridyl sulfide (dps), di-2-pyrimidyl sulfide (dprs)] with AgPF 6 , reacted with dithioethers L 0 [L 0 = 2,6-bis(2-pyridylthiomethyl)pyridine (pytmp), 2,6-bis (2-pyrimidylthiomethyl)pyridine (prtmp) and 2,6-bis{2-(4-methyl) pyrimidylthiomethyl} pyridine (mprtmp)] to afford the compounds [Ru(N,N-L) 2 (N,S-L 0 )][PF 6 ] 2 . The 1 H NMR spectra indicate that L 0 is chelated through S and N atoms with the formation of a four-membered ring. As a consequence, the ruthenium and sulfur atoms are stereogenic centers with D and K and (R) and (S) configurations, respectively. NMR spectra, at low temperatures, show that two invertomers, of similar abundance, as enantiomeric couples DS, KR and DR, KS are present. In the methylene region, four AB systems are observed that in both the species contain two non-equivalent methylene groups. Variable-temperature NMR spectra and EXSY experiments show that the sulfur inversion produces an exchange between the invertomers. The one-dimensional band-shape analysis of the exchanging methylene signals showed that the energy barriers for the process are in the 43-52 kJ mol -1 range. The possible mechanisms of the sulfur inversion are discussed.

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Section: Discussionmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

Fluxional rearrangement in congested ruthenium(II) complexes containing pyrimidine- and/or pyridine-based dithioether ligands

Tresoldí

Pietro

Drommi

et al. 2009

Transition Met Chem

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“…34 Benzylthio complex 39 was used in a mixture MeCN/water at room temperature. 78 1 mol % [Cu] was enough to ensuring a high yield, although only a model reaction was investigated and purification on silica gel was required. In this case, how the active copper(I) species are formed remains uncertain.…”

Section: Reactions Of In Situ Generated Azides and Terminal Alkynesmentioning

confidence: 99%

Well-defined copper(i) complexes for Click azide–alkyne cycloaddition reactions: one Click beyond

Díez‐González

2011

Catal. Sci. Technol.

179

101

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Abstract:The discovery of copper(I) species as excellent catalysts for the regioselective cycloaddition reactions of azides and alkynes served as proof-of-concept of the importance of Click chemistry and opened a broad field of research that has found numerous ramifications in biochemistry, materials and medicinal science, for instance. The use of ligands in this context not only serves to stabilize the oxidation state of copper, but has also been shown to increase and modulate its reactivity. Still, efforts focused on developing more efficient catalytic systems for this transformation remain limited. Herein, the catalytic activities of ligated copper systems are reviewed in a way intended inspirational for further developments.

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“…Related to the phosphines are the N -heterocyclic carbenes, several Cu(I) complexes of which have been described as CuAAC catalysts at elevated temperature in organic solvents [69 -71] . Thiols are a potent poison of the CuAAC reaction in water, but thioethers are an underexplored member of the " soft " ligand class [72] .…”

Section: Catalysts and Ligandsmentioning

confidence: 99%

Copper‐Catalyzed Azide‐Alkyne Cycloaddition (CuAAC)

Finn

Fokin

2010

Catalysis Without Precious Metals

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Introduction1,3 -Dipolar cycloaddition reactions provide direct access to a wide range of useful heterocyclic systems. Many such heterocycles are found in natural products, manmade drugs, agrochemicals, and materials. As " fusion " processes, dipolar cycloadditions are atom -economical, and the variety of readily accessible dipoles and dipolarophiles make these transformations particularly suitable for the synthesis of structurally and functionally diverse collections of compounds. This large family of reactions has been a subject of intensive research, notably by Rolf Huisgen and coworkers, whose work led to the formulation of the general concept of 1,3 -dipolar cycloadditions in 1958 [1] . Since then, dipolar cycloaddition chemistry has found extensive applications in organic synthesis and has been the subject of several reviews [2,3] .Organic azides represent a unique component of cycloaddition processes because R -N 3 is the only 1,3 -dipolar reagent that can be made, handled, and stored as a stable entity. Until recently, the cycloaddition reactions of azides with olefi ns received greater attention among organic chemists than the corresponding reactions with alkynes. Yet, the azide -alkyne combination is uniquely useful for three main reasons. First, the product 1,2,3 -triazole is a remarkably stable aromatic structure that can serve, among other roles, as a structural analogue of a peptide linkage. Second, the azide -alkyne reaction is remarkably slow for a process that is thermodynamically favorable by more than 50 kcal mol − 1 . Finally, azides and alkynes are relatively nonpolar, neither acidic nor basic, and are devoid of substantial hydrogen bonding ability, properties that make them quite " invisible " to and unreactive with most other chemical functionalities in nature and the laboratory. Azides and alkynes can, thereby, be installed on structures that one wishes to link together, and kept in place through many operations of synthesis and elaboration. They are ideal connectors for such a modular approach to synthesis, if effective methods to catalyze their cycloaddition are available. This chapter describes the catalytic role of copper complexes that has allowed this general scheme to be put in operation for a wide array of applications and settings.

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Structures of Copper Complexes of the Hybrid [SNS] Ligand of Bis(2-(benzylthio)ethyl)amine and Facile Catalytic Formation of 1-Benzyl-4-phenyl-1H-1,2,3-triazole through Click Reaction

Cited by 76 publications

References 84 publications

Fluxional rearrangement in congested ruthenium(II) complexes containing pyrimidine- and/or pyridine-based dithioether ligands

Fluxional rearrangement in congested ruthenium(II) complexes containing pyrimidine- and/or pyridine-based dithioether ligands

Well-defined copper(i) complexes for Click azide–alkyne cycloaddition reactions: one Click beyond

Copper‐Catalyzed Azide‐Alkyne Cycloaddition (CuAAC)

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