No abstract

Buzzing with activity: A hydrogen sulfide selective fluorogenic probe, 7-azido-4-methylcoumarin (AzMC), serves as a highly sensitive assay for cystathionine β-synthase activity, and is suitable for the high-throughput discovery of novel enzyme inhibitors.

Cyclopentadienone‐ligated ruthenium complexes, such as Shvo's catalyst, are known to oxidize reversibly alcohols to the corresponding carbonyl compounds. The mechanism of this reaction has been the subject of some controversy, but it is generally believed to proceed through concerted transfer of proton and hydride, respectively, to the cyclopentadienone ligand and the ruthenium center. In this paper we further study the hydride transfer process as an example of a coordinatively directed hydride abstraction by adding quantitative understanding to some features of this mechanism that are not well understood. We find that an oxidant as weak as acetone can be used to re‐oxidize the intermediate ruthenium hydride without catalyst re‐oxidation becoming rate‐limiting. Furthermore, C–H cleavage is a significantly electrophilic event, as demonstrated by a Hammett reaction parameter of ρ = –0.89. We then describe how the application of our mechanistic insights obtained from the study have enabled us to extend the ligand‐directed hydride abstraction strategy to include a rare example of an iron(0) oxidation catalyst.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Buzzing with activity: A hydrogen sulfide selective fluorogenic probe, 7‐azido‐4‐methylcoumarin (AzMC), serves as a highly sensitive assay for cystathionine β‐synthase activity, and is suitable for the high‐throughput discovery of novel enzyme inhibitors.

No abstract