Beyond Click-Chemistry: Transformation of Azides with Cyclopentadienyl Ruthenium Complexes

Efficient conversion of primary azides to aldehydes catalyzed by active site variants of myoglobin

“…Time-dependent studies also showed that the benzyl azide substrate was oxidized at a rate of 250 turnovers/min over the first 10 minutes and completely consumed within 1.5 hours ( SI Figure S2 ). Notably, the product conversion with Mb(H64V,V68A) under these optimized conditions match those reported for the same reaction in the presence of the Mo-based complex 9a at high temperature (100°C) and employing 1,000-fold higher catalyst loadings, thus highlighting the efficiency and mildness of the biocatalytic process in the context of this transformation.…”

“…Interestingly, this reaction sequence is fundamentally distinct from that proposed for azide oxidation mediated by a molybdenum-based catalyst, which requires oxygen and purportedly involves an oxoaziridine and oxime intermediates. 9a …”

“…In particular, this transformation can provide a convenient, alternative route to the installation of aldehydes from a non-oxygenated precursor functional group. Unfortunately, the very few methods currently available to promote this transformation 9 require high catalyst loadings (e.g., 10 mol% MoO 2 (S 2 CNEt 2 ) 2 ) 9a,9b and harsh reaction conditions (reflux in toluene/water mixture) 9a , or they lack of selectivity for formation of the aldehyde product 6c …”

A Study on the Oxygen Vacancies in ZnPd/ZnO‐Al and their Promoting Role in Glycerol Hydrogenolysis

“…After the successful synthesis of the first Cp∧Ru carbene complex, we investigated the possibility of preparing a nitrene/imido complex. Indirect evidence for a Cp∧Ru imido complex was obtained during our studies of the Cp∧Ru‐catalyzed transformation of benzylic azides into hydrobenzamide derivatives, which led to the isolation of mononuclear Ru tetrazene complexes 4a. These species are believed to form via imido complexes 17…”

On the Unique Reactivity of Pd(OAc)2 with Organic Azides: Expedient Synthesis of Nitriles and Imines

“…This result might not seem surprising, owing to the bimolecular nature of this transformation, but several Pd/C catalysts, as well as [Pd 2 (dba) 3 ], actually led to the formation of nitrile 1 a as the major product, even in the absence of solvent. Imines are often observed as minor products in the synthesis of nitriles from azides,16 but, to the best of our knowledge, only a molybdenum-based catalyst has been reported to produce them preferentially 17. As a consequence, we prepared several of these derivatives from different benzylic azides 18.…”