منابع مشابه
Regioselectivity of H Cluster Oxidation
The H(2)-evolving potential of [FeFe] hydrogenases is severely limited by the oxygen sensitivity of this class of enzymes. Recent experimental studies on hydrogenase from C. reinhardtii point to O(2)-induced structural changes in the [Fe(4)S(4)] subsite of the H cluster. Here, we investigate the mechanistic basis of this observation by means of density functional theory. Unexpectedly, we find t...
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Using vo1tammetric technique with a rotating disk electrode, the anodic oxidation of carbazole in aqueous H2S04 ethanol mixtures was shown to proceed under diffusion and electron transfer control conditions. Electro-oxidation involves one electron transfer; electrode passivation occurs due to the formation of a poorly soluble product. By means of the SCF MO LCAO INDO, AMI-UHF and PM3-UHF method...
متن کاملEvidence that the availability of an allylic hydrogen governs the regioselectivity of the Wacker oxidation.
The allylic hydrogen is found to have a dramatic effect on the regioselectivity of the Wacker oxidation, leading to the postulation that an agostic hydrogen or enyl (sigma + pi) complex helps to stabilise the key intermediate.
متن کاملBaeyer–Villiger oxidation of norbornan-7-ones: long-range substituent effects on regioselectivity
Baeyer–Villiger (BV) oxidation is a commonly employed reaction for the transformation of ketones into esters/lactones by organic peroxy acids or hydrogen peroxide. The BV reaction is extensively used since when it is suitably juxtaposed in a synthetic sequence, it can lead to the shortening of carbon chains, amplification of functionality in carbocyclic rings and chains, and transformation of c...
متن کاملEnhancing the efficiency and regioselectivity of P450 oxidation catalysts by unnatural amino acid mutagenesis.
The development of effective strategies for modulating the reactivity and selectivity of cytochrome P450 enzymes represents a key step toward expediting the use of these biocatalysts for synthetic applications. We have investigated the potential of unnatural amino acid mutagenesis to aid efforts in this direction. Four unnatural amino acids with diverse aromatic side chains were incorporated at...
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ژورنال
عنوان ژورنال: Journal of the American Chemical Society
سال: 2011
ISSN: 0002-7863,1520-5126
DOI: 10.1021/ja209165r