One-step entry to olefin-tethered N,S-heterocyclic carbene complexes of ruthenium with mixed ligands

Ding, Nini; Zhang, Wen Hua; Hor, T. S. Andy

doi:10.1039/c2dt12354a

Cited by 21 publications

(7 citation statements)

References 76 publications

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“…One effective strategy is to tailor-design carbene ligands that can stabilise these complexes without hampering their reactivities or redox facility. This can be accomplished through the use of hybrid carbenes [117,187,188] whereby the carbene donor is complemented by a range of other hemilabile donors in proximity so that these donors can act in tandem or synchrony. These donors can switch across a range of coordinative states depending on the need of the metal.…”

Section: Cr(v)-nhc Complexesmentioning

confidence: 99%

N-heterocyclic carbene complexes of Group 6 metals

Wang

Mohamed

et al. 2015

Coordination Chemistry Reviews

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Section: Cr(v)-nhc Complexesmentioning

confidence: 99%

N-heterocyclic carbene complexes of Group 6 metals

Wang

Mohamed

et al. 2015

Coordination Chemistry Reviews

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“…In thiazoles, only one nitrogen atom can be functionalized, in contrast to imidazole for which two nitrogen atoms can be substituted. To the best of our knowledge, NSHC derivatives of thiazole, benzothiazole, and methyl‐thiazole have been reported with only a few metals; the majority were ruthenium(II)25 and palladium(II),26 and a few examples have been obtained for gold(I) and gold(III),27,28 copper(I),29 nickel(II),30 manganese(0),31 cromium(0), and tungsten(0) 32. The replacement of imidazole for the thiazole ring in histidine gives the nonproteinogenic amino acid L ‐thiazolylalanine (ThzAla) 33.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Characterization, and Cytotoxic Activity of Au^I N,S‐Heterocyclic Carbenes Derived from Peptides Containing L‐Thiazolylalanine

et al. 2014

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Thiazolium salts 2a-b derived from a dipeptide Boc-Gly-(Thz-Ala)-OMe (1b) containing the nonproteinogenic amino acid L-thiazolylalanine (Thz-Ala) can be used to generate the corresponding N,S-heterocyclic carbene (NSHC) gold(I) (3ab) and silver(I) (4) complexes. Reaction of the NSHC-gold(I) iodide 3b with Boc-Cys-Gly-OMe gives access to the peptide bioconjugate 5, which contains a NSHC-Au-(S-Cys) unit. Compounds 3-5 constitute the first coin metal NSHC-peptide complexes. All new compounds were comprehensively characterized by 1 H, 13 C and 2D-NMR spectroscopy, IR spec-[a] 2517 (B) (C β,ThzAla H 2 ), 41.3 (A) and 40.9 (B) [C α,Gly (dip)H 2 ], 36.8 (B) and 30.3 (A) (C β,Cys H 2 ), 28.3 (C Boc H 3 ) and 16.4 (NCH 2 CH 3 ) ppm. HRMS (ESI + ): m/z calcd. for [M + H] + 860.2268; found: 860.2292.Cell Culture: Jurkat (leukaemia) and MiaPaca2 (pancreatic carcinoma) cell lines were maintained in RPMI 1640, whereas A549 (lung carcinoma) cells were grown in DMEM (Dulbecco's Modified Eagle's Medium). Both media were supplemented with 5 % fetal bovine serum (FBS), 200 U/mL penicillin, 100 μg/mL streptomycin, and 2 mm l-glutamine. Media for A549 cells were also supplemented with 2.2 g/l Na 2 CO 3 , 100 μg/mL pyruvate, and 5 mL nonessential amino acids (Invitrogen). Cell cultures were maintained in a humidified atmosphere of 95 % air/5 % CO 2 at 37°C. Cytotoxicity Assay by MTT:The MTT assay was used to determine the cell viability as an indicator for the sensitivity of the cells to the complexes. [44] Exponentially growing cells were seeded at a density of approximately 1 ϫ 10 5 cells/mL (A549, MiaPaca2) or 3 ϫ 10 5 cells/mL (Jurkat), in a 96-well flat-bottomed microplate and, after 24 h, they were incubated with the compounds. The complexes were dissolved in DMSO and tested in concentrations ranging from 0.5 to 100 μm and in quadriplicate. Cells were incubated with the test compounds for 24 h at 37°C, then, 10 μL/well of MTT (5 mg/ mL) was added and plates were incubated for 1-3 h at 37°C. Finally, 100 μL/well iPrOH (0.05 m HCl) was added. The optical density was measured at 570 nm using a 96-well multiscanner autoreader (ELISA). The IC 50 was calculated by nonlinear regression analysis using Origin software (Origin Software, Electronic Arts, Redwood City, California, USA).

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“…The known methods, commonly used in the preparation of various alkynylsilanes, are based on two different pathways: namely, silyl functionalization of terminal alkynes via Si–C sp bond formation or incorporation of a whole silylethynyl function (−CCSiR 3 ) with C–C bond creation. The first group includes methods employing the equimolar reactions of various chlorosilanes (SiCl n R 4– n ), alkoxysilanes, or aminosilanes with organometallic species of the type MCCR′ (M = Li, MgX, where X = Cl, Br), as well as those that rely on zinc or zinc salt promoted coupling of terminal alkynes with aminosilanes, chlorosilanes, − Me 3 SiOTf (OTf = −O 3 SCF 3 ) or trisubstituted silanes (SiR 3 H), and comprise also transition-metal-mediated reactions such as terminal alkyne dehydrogenative silylation with hydrosilanes, ruthenium-promoted coupling with chlorosilanes, palladium-catalyzed coupling with SiMe 3 CF 3 , or SiMe 3 OTf …”

Section: Introductionmentioning

confidence: 99%

“…2 The known methods, commonly used in the preparation of various alkynylsilanes, are based on two different pathways: namely, silyl functionalization of terminal alkynes via Si−C sp bond formation or incorporation of a whole silylethynyl function (−CCSiR 3 ) with C−C bond creation. The first group includes methods employing the equimolar reactions of various chlorosilanes (SiCl n R 4−n ), 3 alkoxysilanes, 4 or aminosilanes 5 with organometallic species of the type MCCR′ (M = Li, MgX, where X = Cl, Br), as well as those that rely on zinc or zinc salt promoted coupling of terminal alkynes with aminosilanes, 6a chlorosilanes, 6b−d Me 3 SiOTf 6e (OTf = −O 3 SCF 3 ) or trisubstituted silanes (SiR 3 H), 6f and comprise also transition-metal-mediated reactions such as terminal alkyne dehydrogenative silylation with hydrosilanes, 7 rutheniumpromoted coupling with chlorosilanes, 8 palladium-catalyzed coupling with SiMe 3 CF 3 , 9 or SiMe 3 OTf. 10 On the other hand, the second group comprises methods that use the equimolar reactions of lithium triorganosilylacetylides (Li +− CCSiR 3 ) with a wide range of ketones that lead to the formation of appropriate hydroxyl-functionalized aliphatic silylalkynes, 11 catalytic processes such as palladiumpromoted cross-coupling of various silylalkynes (R 3 SiC CH) 12 and triorganosilylacetylides ([M(CCSiR 3 ) n ]: M = MgX, n = 1; M = In, n = 3; M = ZnCl, n = 1) 13 with halogenofunctionalized organic compounds, or similar nickel-catalyzed reactions 14 yielding silylethynyl-functionalized aryl derivatives.…”

Section: ■ Introductionmentioning

confidence: 99%

Iridium-Promoted Conversion of Chlorosilanes to Alkynyl Derivatives in a One-Pot Reaction Sequence

2014

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By making use of the catalytic potential of the iridium system [{Ir(μ-Cl)(CO) 2 } 2 ]/NEt(i-Pr) 2 in the synthesis of silyl-functionalized alkynes via silylative coupling of terminal alkynes/diynes with iodosilanes, we propose a new protocol allowing employment of various mono-and dichlorosilanes as reagents. The process is based on a sequence of two reactions occurring simultaneously: i.e., conversion of initial chlorosilane (SiR 1 n Cl 4−n ) to the appropriate iodosilane via Cl/I nucleophilic substitution and its further conversion to a silylalkyne derivative ((SiR 1 n (CCR 2 ) 4−n ) via iridium-catalyzed silylative coupling with terminal alkyne. Under optimum conditions, the method has proved to be effective and versatile in the conversion of a wide range of chlorosilanes to a rich portfolio of various corresponding alkynyl-functionalized silicon derivatives. Additionally, NMR studies of the equimolar reaction of a well-defined iridium(I) alkynyl precursor with Me 3 Si−I revealed that Si−I bond activation in iodosilane molecules occurred via oxidative addition to the iridium center.

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One-step entry to olefin-tethered N,S-heterocyclic carbene complexes of ruthenium with mixed ligands

Cited by 21 publications

References 76 publications

N-heterocyclic carbene complexes of Group 6 metals

N-heterocyclic carbene complexes of Group 6 metals

Synthesis, Characterization, and Cytotoxic Activity of Au^I N,S‐Heterocyclic Carbenes Derived from Peptides Containing L‐Thiazolylalanine

Iridium-Promoted Conversion of Chlorosilanes to Alkynyl Derivatives in a One-Pot Reaction Sequence

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One-step entry to olefin-tethered N,S-heterocyclic carbene complexes of ruthenium with mixed ligands

Cited by 21 publications

References 76 publications

N-heterocyclic carbene complexes of Group 6 metals

N-heterocyclic carbene complexes of Group 6 metals

Synthesis, Characterization, and Cytotoxic Activity of AuI N,S‐Heterocyclic Carbenes Derived from Peptides Containing L‐Thiazolylalanine

Iridium-Promoted Conversion of Chlorosilanes to Alkynyl Derivatives in a One-Pot Reaction Sequence

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Synthesis, Characterization, and Cytotoxic Activity of Au^I N,S‐Heterocyclic Carbenes Derived from Peptides Containing L‐Thiazolylalanine