Studien zum Vorgang der Wasserstoffübertragung, XII: Hydrierende Spaltung von Sulfonen mit Tetramethylammonium als Elektronenüberträger

Horner, L.; Neumann, Heinz

doi:10.1002/cber.19650980606

Cited by 76 publications

(15 citation statements)

References 16 publications

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“…Ammonium salts (cation: tetraalkyl ammonium) may be formed at much more negative potentials and ammonium amalgams R 4 N(Hg) n can be used in situ [1] as powerful reducing reagents. More recently, electroactive materials were shown to be produced electrochemically with some post-transition metals used as cathode materials with quaternary ammonium salts.…”

Section: Accepted M Manuscriptmentioning

confidence: 99%

Electron transfer at platinum and palladium interfaces in super-dry electrolytes. Generation of iono-metallic layers. A mini-review

Simonet¹

2015

Electrochemistry Communications

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Metallic electrodes (gold, platinum) have been considered for long as inert and quasiideal electrodes both within the anodic and cathodic ranges. Here are gathers some striking evidences of the reactivity of platinum (and accessorily that of palladium) in aprotic polar solvents (water present < 200 ppm) for leading, by cathodic reaction with present electrolytes, to a large panel of iono-metallic layer. These modified metals layers may present many interesting behaviours: reductions via electron transfer, insertion by exchange of charged organic species inside the metallic matrix, catalysis, energy storage, etc… The highly foreseeable interest of those new materials and interfaces is briefly underlined in this mini-review.

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Section: Accepted M Manuscriptmentioning

confidence: 99%

Electron transfer at platinum and palladium interfaces in super-dry electrolytes. Generation of iono-metallic layers. A mini-review

Simonet¹

2015

Electrochemistry Communications

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“…This is the reason why partially tosylated products were found and the yields were sometimes relatively low. Only in one case we have studied the detosylation by electrochemical means as described by Horner et al [21] for open-chain tosylamides. The main difficulty in this method was that the protected derivatives are only slightly soluble in polar solvents such as CH30H so that we had to work with a suspension of the starting compound.…”

Section: Preparation Of 4-(2-cyanoethyl)-l 7 Il-tritosyl-i 4 7ilmentioning

confidence: 99%

Metal complexes with macrocyclic ligands, XVII. Synthesis of two key intermediates for the preparation of mono‐N‐functionalized tetraazamacrocycles and their metal complexes

Hediger

Kaden

1983

Helvetica Chimica Acta

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SummaryWith a modification of the cyclization procedure of Richman & Atkins [8] the two macrocycles 1,4,7-tritosyl-ll-benzyl-l, 4,7,1l-tetraazacyclotetradecane (8) and 1,7,ll-tritosyl-4-trityl-l, 4,7,1l-tetraazacyclotetradecane (15) were prepared. After selective cleavage of the benzyl and trityl group, respectively, one obtains the two key products 1,4,7-tritosyl-1,4,7,ll-tetraazacyclotetradecane (9) and 1,7,1 l-tritosyl-lI4,7,1l-tetraazacyclotetradecane (16) which have three N-atoms protected by tosyl groups and one accessible for further reactions. To test some of the possibilities we have alkylated 9 and 16 with iodoacetamide, 1-tosyl-aziridine and acrylonitrile. After detosylation with HBr in glacial acetic acid in the presence of phenol mono-N-functionalized tetraazamacrocycles were thus obtained.Theadvantage of this synthesis is that the cyclization which is the most difficult step of the whole procedure, has to be done only once, regardless of the nature of the pendant arm. In addition a large number of derivatives can be prepared by varying the alkylation component.With Ni2+, Cu2+ and Zn2+ metal complexes of these new ligands were prepared and their IR. and VIS. spectra studied. In the case of the carbamoyl derivatives 12, 14 and 18 the Cu2+-complexes exist in two forms. Whereas at low pH the carboxamide group of the pendant arm is probably not bound to the metal ion, at high pH after deprotonation it coordinates in one of the axial positions.In contrast to open-chain ligands tetraazamacrocycles often form kinetically stable complexes even with metal ions which give tipically labile complexes [2]. This allows to study these metal complexes in strongly acidic or alkaline solutions. Moreover it is often also possible to assume that the coordination geometry and stoichiometry remains the same in the solid state and in solution. Thus one can study and correlate structures and reactivities in a simple way, similarly to what has been done for the kinetically stable Cr (111) and Co (111) complexes. 1)Part XVI, see [I]. 2,

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“…It has been known for more than 50 years 26 that the formal precursors to sulfinates, (hetero)aryl sulfones, can also act as a source of alkyl radicals, albeit under different initiation manifolds. Their utility in reductive initiation has proven successful, 27 , 28 although largely untested in aqueous media until their recent use in modification of biomolecules bearing unnatural amino acid residues.…”

Section: Resultsmentioning

confidence: 99%

Residue-Selective Protein C-Formylation via Sequential Difluoroalkylation-Hydrolysis

Imiołek

Isenegger

et al. 2021

ACS Cent. Sci.

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The carbonyl group is now a widely useful, nonproteinogenic functional group in chemical biology, yet methods for its generation in proteins have relied upon either cotranslational incorporation of unnatural amino acids bearing carbonyls or oxidative conversion (chemical or enzymatic) of existing natural amino acids. If available, alternative strategies for directly adding the CO group through C–C bond-forming C-carbonylation, particularly at currently inaccessible amino acid sites, would provide a powerful method for adding valuable reactivity and expanding possible function in proteins. Here, following a survey of methods for HCF2· generation, we show that reductive photoredox catalysis enables mild radical-mediated difluoromethylation-hydrolysis of native protein residues as an effective method for carbonylation. Inherent selectivity of HCF2· allowed preferential modification of Trp residues. The resulting C-2-difluoromethylated Trp undergoes Reimer-Tiemann-type dehalogenation providing highly effective spontaneous hydrolytic collapse in proteins to carbonylated HC(O)-Trp (C-formyl-Trp = CfW) residues. This new, unnatural protein residue CfW not only was found to be effective in bioconjugation, ligation, and labeling reactions but also displayed strong “red-shifting” of its absorption and fluorescent emission maxima, allowing direct use of Trp sites as UV–visualized fluorophores in proteins and even cells. In this way, this method for the effective generation of masked formyl-radical “HC(O)·” equivalents enables first examples of C–C bond-forming carbonylation in proteins, thereby expanding the chemical reactivity and spectroscopic function that may be selectively and post-translationally “edited” into biology.

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Studien zum Vorgang der Wasserstoffübertragung, XII: Hydrierende Spaltung von Sulfonen mit Tetramethylammonium als Elektronenüberträger

Cited by 76 publications

References 16 publications

Electron transfer at platinum and palladium interfaces in super-dry electrolytes. Generation of iono-metallic layers. A mini-review

Electron transfer at platinum and palladium interfaces in super-dry electrolytes. Generation of iono-metallic layers. A mini-review

Metal complexes with macrocyclic ligands, XVII. Synthesis of two key intermediates for the preparation of mono‐N‐functionalized tetraazamacrocycles and their metal complexes

Residue-Selective Protein C-Formylation via Sequential Difluoroalkylation-Hydrolysis

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