Crystal structure, side product

The crystal structures of PbTX-1 dimethyl acetal, PbTX-1, and dihydro PbTX-1 provide a total of four independent pictures of the same brevetoxin skeleton. It is rare that this quantity of structural data is available for a natural product of this size. A comparison of torsional angles shows that all four molecules have approximately the same conformations in all rings, except, of course, for the aldehyde side chain and the E-ring in one of the independent molecules of PbTX-1. Least squares superposition fits among the four molecules gave the following average distances ... 

British Biotech has described co-crystal structures of both BB-3497 and actinonin bound in the active site of E. coli PDF [24]. The metal centre (Ni ) in both complexes adopts a pentacoordinate geometry, bound by the two oxygen atoms of the hydroxamate along with Cys-90, His-132 and His-136. This coordination pattern is consistent with the mechanism of de-formylation proposed by Becker et al. [56] and Jain et al. [67], in which a pentacoordinated metal centre stabilises the transition state during hydrolysis of the formamide bond. When compared to the co-crystal structure of a substrate hydrolysis product, Met-Ala-Ser, it is clear that the side chains of these two inhibitors bind into the active site pockets similarly to the substrate [56]. 

Dopamine /3-hydroxylase (D/3H) is a copper-containing glycoprotein that hydroxylates dopamine at the benzylic position to norepinephrine.84 During the attempted crystallization of the bis(hydroxide)-bridged dicopper(II) dimer, a side product was subsequently isolated (complex (63)), revealing intramolecular hydroxylation at a formally benzylic position of the tris(imidazo-lyl)phosphine ligand.85 The copper(II) center has an axially compressed TBP structure. 

Ogura and coworkers178,179 continued their study of the addition of lithiated heterocycles to 2,3 5,6-di-0-isopropylidene-L-gulono-l,4-lactone (50) and related compounds. In the case of the addition of lithiated 1,3-dithiane to 50, it was shown178 by X-ray crystal-structure analysis that l-(l,3-dithian-2-yl)-2,3 5,6-di-0-isopropylidene-/3-L-gulofuranose is R at the anomeric carbon atom. This demonstrates that the product of this reaction is, surprisingly, the more sterically hindered of the two products possible. This is the opposite of that predicted for addition of the lithiated dithiane from the less hindered side of 50 if no equilibration of the initial adduct is involved. 

The removal of side products such as EG, A A, CO2, water and oligomers is controlled by the physics of mass transport in the solid state. This mechanism correlates with particle size, density, crystallinity, crystal structure and perfection, and surface conditions, as well as the desorption of the reaction products from... 

It should be pointed out that the crystal size and the surface structure may also affect the desorption of side products. The development of crystallinity... 

Moreover, in deprotonation reactions with common alkyllithium bases (e.g. butyl-lithium), no side-products are formed, that increase the solubility of the polylithium compound. Also, product mixtures are only rarely observed with this method. Thus, the resulting polylithium compound can be isolated or crystallized more easily. This is why—in addition to Section II. E—only this section presents many visualizations of successful X-ray structural analyses of polylithiated compounds. 

These add to aldehydes providing the homoaldol products 351 with high stereoselectivity following the expected stereochemical course, as could be elucidated by several X-ray crystal structure analyses under anomalous dispersion (equation 93). It is currently unknown why the yields are relatively low (21-35%), since we could not detect side products besides traces of starting material. The corresponding lithium-TMEDA complexes, after titanation, deliver good yields (71-79%). The homoaldol products are easily converted to enantioenriched bicyclic y-lactones of type 352 °. 

The separation of this dicyclohexylurea urea is relatively laborious, that is, it has to be conducted by chromatography or crystallization. After the activation of carboxylic acid with carbodiimide B and subsequent acylation of a heteroatom nucleophile, one certainly obtains a urea as a side product, too. It has the structure C and thus is an amine, the separation of which can, however, be accomplished easily by extraction with aqueous hydrochloric acid. 

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