Acetylene hydratase is a tungsten-dependent enzyme that catalyzes the nonredox hydration of acetylene to acetaldehyde. Density functional theory calculations are used to elucidate the reaction mechanism of this enzyme with a large model of the active site devised on the basis of the native X-ray crystal structure. Based on the calculations, we propose a new mechanism in which the acetylene subs...

An enantioselective total synthesis of (-)-galiellalactone has been accomplished. The key features of the synthesis involve the highly stereoselective construction of the cis-trisubstituted cyclopentane intermediate by a Pd(0)-catalyzed cyclization, the stereospecific introduction of an angular hydroxyl group by Riley oxidation, and the efficient construction of the tricyclic system of (-)-gali...

Herein, we report the use of acid/base complexes for the ring opening polymerization of (L)-lactide. The salt formed from an equimolar reaction of benzoic acid and DBU produced a catalyst capable of controlled polymerizations allowing for targeted molecular weights and narrow polydispersities. The use of computational analysis suggests a bifunctional catalytic mechanism wherein both the monomer...

The acylation of alcohols catalyzed by N,N-dimethylamino pyridine (DMAP) is, despite its widespread use, sometimes confronted with substrate-specific problems: For example, target compounds with multiple hydroxy groups may show insufficient selectivity for one hydroxyl, and the resulting product mixtures are hardly separable. Here we describe a concept that aims at tailor-made catalysts for the...

The title compound, C(10)H(13)NO(3), was obtained as a by-product of the aldolization reaction of furo[3,4-c]pyridin-3(1H)-one with thio-phene-2-carboxaldehyde. The substituents on the pyridine ring are nearly coplanar, with an 8.1 (2)° rotation of the hydroxmethyl group from this plane. The mol-ecules assemble in the crystal structure as chains via O-H⋯N hydrogen bonding between the pyridine N...

The sulfonylcarbamate group is a unique hydroxyl protecting group. In contrast to typical acyl protecting groups, the sulfonylcarbamate group is stable under harsh basic conditions, while showing labile behavior under mild basic conditions. Its compatibility with other hydroxyl protecting groups and application to carbohydrate chemistry is demonstrated.

The rotationally resolved LIF spectra of four different isotopomers of the phenol--nitrogen cluster have been measured to elucidate the structural parameters of the cluster in ground and electronically excited (S1) state. The fit of the rotational constants has been performed by a genetic algorithm and by an assigned fit to the line frequencies. The results of both methods are compared. The int...