Artificial model for cystathionine β-synthase: efficient β-replacement reaction with thiols employing a novel pyridoxal model compound having an imidazole function

As a second-generation pyridoxal model compound for cystathionine β-synthase, we designed a novel model compound having an ionophore function and an imidazole function, application of which to the β-replacement reaction with various thiols smoothly took place to give S-substituted cysteines. Peptides having a serine-O-carbonate residue at the N-terminal position were also converted to the corresponding peptides having an S-substituted cysteine residue under the catalytic conditions of the novel pyridoxal model compound.     

Characteristics of organic transformations in a confined dendritic core: studies on the AIBN-initiated reaction of dendrimer cobalt(II) porphyrins with alkynes

Cobalt(II) complexes of poly(aryl ester) dendrimer porphyrins [(m-[Gn]TPP)Co(II)] (generation number n=0-4), in the presence of azobisisobutyronitrile (AIBN) at 60 degrees C, underwent alkenylation with several alkynes at the metal center. A complete inhibition of double-bond migration (secondary transformation) was observed for [(m-[Gn]TPP)Co(II)] (n=3 and 4), which gave [(m-[Gn]TPP)Co(III)-C(=CH(2))R] (n=3 and 4) exclusively. Overall reaction rates for [(m-[Gn]TPP)Co(II)] (n=0-3) were hardly dependent on the size of the dendritic substituents, while a notable retardation was observed for the largest dendrimer, [(m-[G4]TPP)Co(II)]. Mechanistic studies on double-bond migration with pure [(m-[Gn]TPP)Co(III)-C(=CH(2))Bu] (n=0-4) demonstrated that the secondary transformation involves participation of [(m-[Gn]TPP)Co(III)H] (n=0-4), derived from [(m-[Gn]TPP)Co(II)] and AIBN, rather than [(m-[Gn]TPP)Co(II)] alone. Crossover experiments using [(m-[Gn]TPP)Co(III)-C(=CH(2))Bu] (n=2-4), in combination with nondendritic [(m-[G0]TPP)Co(II)] and AIBN, indicated a high level of steric protection of the active center by a robust [G4]-dendritic cage, as suggested by a (1)H NMR pulse relaxation time profile of m-[G4]TPPH(2).     

Artificial model for cystathionine β-synthase: construction of a catalytic cycle with a pyridoxal model compound having an ionophore function

Catalytic transformation of serine-O-carbonate to S-aryl cysteine derivatives was successfully achieved in the presence of Li⁺ by the use of a pyridoxal model compound having an ionophore function, which is the first example mimicking cystathionine β-synthase, artificially.     

On the Evolutionary History of the Twenty Encoded Amino Acids

α-Amino acids are essential molecular constituents of life, twenty of which are privileged because they are encoded by the ribosomal machinery. The question remains open as to why this number and why this 20 in particular, an almost philosophical question that cannot be conclusively resolved. They are closely related to the evolution of the genetic code and whether nucleic acids, amino acids, and peptides appeared simultaneously and were available under prebiotic conditions when the first self-sufficient complex molecular system emerged on Earth. This report focuses on prebiotic and metabolic aspects of amino acids and proteins starting with meteorites, followed by their formation, including peptides, under plausible prebiotic conditions, and the major biosynthetic pathways in the various kingdoms of life. Coenzymes play a key role in the present analysis in that amino acid metabolism is linked to glycolysis and different variants of the tricarboxylic acid cycle (TCA, rTCA, and the incomplete horseshoe version) as well as the biosynthesis of the most important coenzymes. Thus, the report opens additional perspectives and facets on the molecular evolution of primary metabolism.     

Radical and Electron Recycling in Catalysis

An increasing number of enzymes are being discovered that contain radicals or catalyze reactions via radical intermediates. These radical enzymes are able to open reaction pathways that two‐electron steps cannot achieve. Recently, organic chemists started to apply related radical chemistry for synthetic purposes, whereby an electron energized by light is recycled in every turnover. This Minireview compares this new type of reaction with enzymes that use recycling radicals and single electrons as cofactors.     

四氢叶酸辅酶参与的酶催化—碳单元转移反应及其人工模拟进展

简要介绍了生物体系中酶催化的一碳单元转移反应以及四氢叶酸辅酶的结构和作用,综述了一碳单元转移反应的人工模型进展,展望了上述反应的理论研究方法及前景。     

Synthese und Anwendung von stereospezifisch mit Tritium oder Deuterium markierter Mevalonsäure

Nach einer allgemeinen Einführung in das Problem der Prochiralität gibt die Arbeit einen Überblick über die Möglichkeiten zur chemischen und enzymatischen Synthese stereospezifisch mit Deuterium bzw. Tritium markierter Mevalonsäure. Anschließend werden die wichtigsten Arbeiten zur Anwendung dieser markierten Mevalonsäuren diskutiert.