Aromatization of arene 1,2-oxides. 1,2-Oxides of methyl phenylacetate and methyl trans-cinnamate

Chao, Herbert S. I.; Berchtold, Glenn A.

doi:10.1021/jo00319a029

Cited by 19 publications

(5 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The synthesis of the complexes employed in this study was carried out using the methodology previously described to modify the RAPTA scaffold, depicted in Scheme 1. 9 Briefly, 2-(cyclohexa-1,4-dien-1-yl)acetic acid, 1, obtained via a Birch reduction of phenyl acetic acid, 28 was coupled to the appropriate chiral amine, either R-or S-methylbenzylamine, 2-(R) or 2-(S), with the aid of TBTU (O-(benzotriazol-1-yl)-N,N,N′,N′tetramethyluronium tetrafluoroborate), which suppresses racemisation. 29 An excess of the diene, 3-(R) or 3-(S), was then heated to reflux in EtOH with RuCl 3 to give the dimeric Ru(II) complexes 4-(R) or 4-(S) as orange solids in good yields.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Ruthenium(ii) arene PTA (RAPTA) complexes: impact of enantiomerically pure chiral ligands

et al. 2013

View full text Add to dashboard Cite

Organometallic ruthenium(II) arene complexes containing the PTA ligand ([Ru(η(6)-arene)Cl(2)(PTA)], PTA = 1,3,5-triaza-7-phosphatricyclo-[3.3.1.1]decane, termed RAPTA) show pharmacologically relevant anti-tumour properties in vitro. Two new enantiomeric pairs of RAPTA compounds, containing the chiral arene (R)- or (S)-2-phenyl-N-(1-phenylethylene)acetamide and either dichlorido or oxalato ligands were synthesised and fully characterised. The stability of the complexes towards hydrolysis was assessed and the dichlorido complexes were found to be more stable towards hydrolysis than the prototype complex RAPTA-C, ([Ru(η(6)-p-cymene)Cl(2)(PTA)]). The cytotoxicity of the compounds towards human ovarian cancer cells is moderate to good with a degree of selectivity towards the cancer cells over healthy cells. More significantly, for the first time we were able to establish the influence of a bulky, chiral group attached to the arene on the cytotoxicity of this class of compound, with the S-enantiomer being more cytotoxic than the R-enantiomer.

show abstract

Section: Resultsmentioning

confidence: 99%

“…PTA (1,3,5-triaza-7-phosphatricyclo-[3.3.1.1]decane), 36 2-(cyclohexa-1,4-dien-1-yl)acetic acid, 1 28 and silver oxalate 12 were synthesised according to literature procedures. All other reagents were purchased from commercial sources and used without further purification.…”

Section: Methodsmentioning

confidence: 99%

Ruthenium(ii) arene PTA (RAPTA) complexes: impact of enantiomerically pure chiral ligands

et al. 2013

View full text Add to dashboard Cite

show abstract

“…26 Synthesis of the phenylacetic acids started with the conversion of pbromotoluene ( 14) and 3,5-dibromotoluene (15) into Grignard reagents and treating them with D 2 O to obtain toluene-4-d ( 16) 27 and toluene-3,5-d 2 (17). 28 A radical bromination of these toluenes and commercial toluene-d 8 (18), followed by reaction with NaCN 29 and hydrolysis 24 yielded (phenyl-4-d)acetic (19), 30 (phenyl-3,5-d 2 )acetic (20), 28 and (phenyl-d 5 )acetic ( 21) 24 acids.…”

Section: ■ Resultsmentioning

confidence: 99%

Phenyl-Substituted Cibalackrot Derivatives: Synthesis, Structure, and Solution Photophysics

et al. 2023

View full text Add to dashboard Cite

Three symmetrically and three unsymmetrically substituted cibalackrot (7,14-diphenyldiindolo[3,2,1-de:3′,2′,1′-ij][1,5]naphthyridine-6,13-dione, 1) dyes carrying two derivatized phenyl rings have been synthesized as candidates for molecular electronics and especially for singlet fission, a process of interest for solar energy conversion. Solution measurements provided singlet and triplet excitation energies and fluorescence yields and lifetimes; conformational properties were analyzed computationally. The molecular properties are close to ideal for singlet fission. However, crystal structures, obtained by single-crystal X-ray diffraction (XRD), are rather similar to those of the polymorphs of solid 1, in which the formation of a charge-separated state followed by intersystem crossing, complemented with excimer formation, outcompetes singlet fission. Results of calculations by the approximate SIMPLE method suggest which ones among the solid derivatives are the best candidates for singlet fission, but it appears difficult to change the crystal packing in a desirable direction. We also describe the preparation of three specifically deuteriated versions of 1, expected to help sort out the mechanism of fast intersystem crossing in its charge-separated state.

show abstract

“…Ru(II) arene dimers were prepared according to literature procedures. 25 Methyl-tri-O-acetyl-2-amino-2-deoxy-β-D-glucopyranoside, 26 2-(cyclohexa-1,4dien-1-yl)acetic acid, 27 and silver oxalate 28 were prepared according to the literature. Synthetic details and characterization of precursors [Ru(PAG)Cl 2 ] 2 are reported in the Supporting Material.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Ruthenium(II)–Arene Complexes with Glycosylated NHC-Carbene Co-Ligands: Synthesis, Hydrolytic Behavior, and Binding to Biological Molecules

et al. 2023

View full text Add to dashboard Cite

Ruthenium(II) complexes with a three-legged piano-stool structure based on an arene ring, an N-heterocyclic carbene (NHC)-carbene ligand with a peracetylated glucose moiety and two chlorides or one bidentate ligand, were prepared and characterized by spectroscopy and crystallography. In one case, the sugar substituent is replaced by an ethyl. The chirality of the sugar results in the formation of two diastereomers that interconvert through rotations around the Ccarbene–Ru and Carene–Ru bonds. In water, the complexes undergo a series of equilibrium hydrolysis steps involving the Ru–Cl bonds. The Ru–arene bond and the sugar acetyls are also partially hydrolyzed, and the selectivity of the process is governed by the nature of the arene and the pH of the solution. The reactivity of the compounds was studied against model nucleophiles and biological macromolecules. In the former case, mass experiments demonstrated a variety of binding modes with a trend reflecting the stability in aqueous environment. In the latter case, protein crystallography was used to characterize the preferential binding sites of one of the complexes. The X-ray structure of the adduct formed upon reaction of one representative complex with hen egg white lysozyme contains a Ru center, which retains the carbene ligand, close to the side chain of Asp119. In the adduct with bovine pancreatic ribonuclease, there are two protein molecules in the asymmetric unit. In one molecule, two Ru centers are located close to the side chains of His105 and of His119, which is the protein active site. In the second molecule, only one Ru center was found in the proximity of the side chain of His105. The Ru complexes also interact with calf-thymus DNA, although without displacing the intercalating probe EB. Finally, the complexes are essentially inactive against the human ovarian carcinoma A2780 cells, the cisplatin-resistant A2780cis cells, and the human embryonic kidney HEK293T cells.

show abstract

Aromatization of arene 1,2-oxides. 1,2-Oxides of methyl phenylacetate and methyl trans-cinnamate

Cited by 19 publications

References 0 publications

Ruthenium(ii) arene PTA (RAPTA) complexes: impact of enantiomerically pure chiral ligands

Ruthenium(ii) arene PTA (RAPTA) complexes: impact of enantiomerically pure chiral ligands

Phenyl-Substituted Cibalackrot Derivatives: Synthesis, Structure, and Solution Photophysics

Ruthenium(II)–Arene Complexes with Glycosylated NHC-Carbene Co-Ligands: Synthesis, Hydrolytic Behavior, and Binding to Biological Molecules

Contact Info

Product

Resources

About