Alcohol‐Induced C−N Bond Cleavage of Cyclometalated N‐Heterocyclic Carbene Ligands with a Methylene‐Linked Pendant Imidazolium Ring

Reaction of the pentamethylcyclopentadienyl rhodium iodide dimer [Cp*RhI₂]₂ with 1,1′‐diphenyl‐3,3′‐methylenediimidazolium diiodide in non‐alcohol solvents, in the presence of base, led to the formation of bis‐carbene complex [Cp*Rh(bis‐NHC)I]I (bis‐NHC=1,1′‐diphenyl‐4,4′‐methylenediimidazoline‐5,5′‐diylidene). In contrast, when employing alcohols as the solvent in the same reaction, cleavage of a methylene C?N bond is observed, affording ether‐functionalized (cyclometalated) carbene ligands coordinated to the metal center and the concomitant formation of complexes with a coordinated imidazole ligand. Studies employing other 1,1′‐diimidazolium salts indicate that the cyclometalation step is a prerequisite for the activation/scission of the C?N bond and, based on additional experimental data, a S_N2 mechanism for the reaction is tentatively proposed.     

Structural Manipulation of Ruthenium(II) Polypyridine Nitrone Complexes to Generate Phosphorogenic Bioorthogonal Reagents for Selective Cellular Labeling

We report a new class of ruthenium(II) polypyridine complexes functionalized with a nitrone group as phosphorogenic bioorthogonal probes. These complexes were very weakly emissive owing to rapid C=N isomerization of the nitrone moiety, but exhibited significant emission enhancement upon strain‐promoted alkyne–nitrone cycloaddition (SPANC) reaction with bicyclo[6.1.0]nonyne (BCN)‐modified substrates. The modification of nitrone with a dicationic ruthenium(II) polypyridine unit at the α‐C‐position and a phenyl ring at the N‐position led to remarkably accelerated reaction kinetics, which are substantially greater (up to ≈278 fold) than those of other acyclic nitrone–BCN systems. Interestingly, the complexes achieved specific cell membrane/cytosol staining upon specific labeling of an exogenous substrate, BCN‐modified decane (BCN‐C10), in live cells. Importantly, the in situ generation of the more lipophilic isoxazoline adduct in the cytoplasm resulted in increased cytotoxicity, highlighting a novel approach to apply the SPANC labeling technique in drug activation.     

Selective cleavage of the linear ether bond in benzyl glycidyl ether and triphenylmethyl glycidyl ether by potassium alkalide as two-electron-transfer reagent

The linear ether bond was exclusively cleaved in benzyl glycidyl ether and triphenylmethyl glycidyl ether under the influence of K⁻, K⁺(15-crown-5)₂ (1), whereas the strongly strained three-membered oxacyclic ring remained undisturbed. Potassium glycidoxide and benzylpotassium were found as the primary reaction products of benzyl glycidyl ether with 1. Subsequently, benzylpotassium reacted with benzyl glycidyl ether giving the next potassium glycidoxide molecule and bibenzyl. Benzyl phenyl ether was used as a model compound to explain the mechanism of bibenzyl formation. The reaction of triphenylmethyl glycidyl ether with 1 resulted in potassium glycidoxide and stable triphenylmethylpotassium. After treating with a quenching agent a new glycidyl ether or glycidyl ester was obtained from potassium glycidoxide. These results were found when the reaction occurred at the excess of glycidyl ether. In another case, i.e. at the excess of 1 further reactions took place with the participation of potassium anions and various new compounds were observed in the reaction mixture after benzylation or methylation. Thus, the method of substrates delivery influences the course of studied processes in a decisive way.     

A new strategy for solid phase synthesis of a secondary amide library using sulfonamide linker via radical traceless cleavage

A new strategy for solid phase synthesis of a secondary amide library using sulfonamide linker via radical traceless cleavage is reported. Polystyrylsulfonyl chloride (1) reacted with primary amines to afford polystyryl-supported N-alkyl sulfonamides (2), which were acylated with acid chlorides and followed by radical cleavage with TiCl₄/Zn to afford secondary amides. It was interestingly found that the products released from acyl alkanesulfonamide resins are closely dependent on the substituents of benzene rings of alkyl or acyl groups on the resins. When the substituent on benzene ring of N-benzyl group of sulfonamides is an electron rich MeO-group, the products released from sulfonamide resins are dependent on the substitution position on benzene ring: para-MeO- to yield 1,2-bis (p-methoxylphenyl)ethane and N-p-methoxylbenzyl benzamide (30:1); ortho-MeO- to give 1,2-bis (o-methoxylphenyl)ethane and N-o-methoxylbenzyl benzamide (1:15); and meta-MeO- only to release N-m-methoxylbenzyl benzamide. Neither N-benzoyl sulfonamide resins on benzene ring with electron-drawing para-O₂N-, nor the one with electron-donating para-H₂N- could release any amide product, while the N-benzoyl sulfonamide resins on benzene ring with para-acetamido group released para-acetamidobenzamides. The conjugation effect to stabilize the radical groups in the radical cleaving process was observed.     

Anodic oxidation of a tetrasubstituted cyclooctatetraene. Multiple carbon-carbon bond cleavage and aromatization

Anodic oxidation of 1,2-,5,6-bis[trimethylene]cyclooctaetraene in methanol affords as the major product a substance formed by a complex sequence of carbon-carbon bond cleavages and concomitant aromatization.     

Thermo-cleavable polymers: Materials with enhanced photochemical stability

Photochemical stability of three thermo-cleavable polymers was investigated as thin films under atmospheric conditions. A significant increase in lifetime was observed once the side-chain was cleaved emphasizing the detrimental effect of solubilizing groups on the photochemical stability of conjugated polymers. In addition to their ease of processing, thermo-cleavable polymers thus also offer a greater intrinsic stability under illumination.     

Site-specifically Hydrolytic Cleavage of Oxidized Insulin B Chain With Cu(II) Ion

Selectively chemical cleavage of peptides and proteins is one of the most important reactions in both chemical and biochemical processes. Over the past decade, the interaction of palladium(II) complexes with methionine, cysteine and histidine-containing peptides and proteins and the hydrolytic cleavage of the corresponding amide bond by Pd(II) complexes have been extensively studied1-13. However, reports concerning the directly selective hydrolysis of peptides and proteins with other simple …     

Cleavage of polystyrene‐b‐poly(ethylene oxide) block copolymers with a trithiocarbonate linkage in solutions

In this work, the polystyrene‐b‐poly(ethylene oxide) (PS‐b‐PEO) block copolymers with a trithiocarbonate group between the blocks were prepared by polymerization of styrene in the presence of a trithiocarbonate reversible addition fragmentation chain transfer (RAFT) agent connected with PEO. Decomposition of the trithiocarbonate group by UV irradiation was investigated in three different types of solvent: tetrahydrofuran (THF, common solvent for both blocks), cyclohexane/dioxane mixture (selective solvent for the PS block) and N,N‐dimethylformamide (DMF)/ethanol mixture (selective solvent for the PEO block). It is found that cleavage of the block copolymers can take place in all these three solvents and the cleavage ratio ranges from 76 to 86%. The micellar morphologies in selective solvents before and after cleavage were examined. It is observed that the size of the micelles is reduced after cleavage and sometimes aggregation of the micelles occurs due to removal of the corona of micelles. It shows that this work provides a facile and general method for synthesis of cleavable block copolymers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3834–3840, 2010