Syntheses du tri-O-benzyl-3,4,6-D-glucal

The synthesis of 3,4,6 tri-O-benzyl-D-glucal (4) has been accomplished by direct benzylation of triacetylglucal (yield 55%) and by zinc reduction of 3,4,6-tri-O-henzyl-2-acetoxy-1-bromoglucose (yield 26%). The nmr spectra of tribenzyl- and triacetyl-D-glucal in the presence of lanthanide shift reagents were reported.     

Photocycloaddition of Cyclohex‐2‐enones to Penta‐1,2,4‐triene

Dihydrothiinone 9a undergoes photocycloaddition regioselectively to all three C?C bonds of penta‐1,2,4‐triene ( 10 ), the relative stabilities of the biradical intermediates determining the product distribution. In contrast, cyclohexenone 9b and dihydropyranone 9c afford more complex mixtures of bicyclo[4.2.0]octanones, which also turn out to be less stable on chromatographic workup, reflecting the higher strain due to the shorter bond lengths (C? O and C? C vs. C? S) in the six‐membered rings, respectively.     

Säurekatalysierte Umlagerungen von 1,5-Dimethyl-6-methyliden-tricyclo[3.2.1.02,7]oct-3-en-8endo-olen

Acid Catalysed Rearrangement of 1,5-Dimethyl-6-methyliden-tricyclo[3.2.1.0^2,7]oct-3-en-8endo-ols The tricyclic alcohols 2,3,4 and 6 (Scheme 1) are synthesized by the reaction of the tricyclic ketone 1 with sodiumborohydrid or metalloorganic reagents. Their configuration at C(8) is determined by NMR. in the presence of Eu(fod)₃. The exo-attack of 1 by the nucleophil forming the endo-alcohol is favored, the π-electrons of C(3) = C(4) hindering the endo-attack. On treatment with sulfuric acid in dioxane/water at 25° the tertiary alcohols yield aryl-substituted ketones. 3 gives in 78.5% yield a mixture of the 3-(dimethylphenyl)-2-butanones 12 and 13 , in addition to 16.5% of (2,3,4-trimethylphenyl)-2-propanon ( 14 ) (Scheme 2). The alcohols 4 and 6 yield mixtures of the 2-(dimethylphenyl)-3-pentanones 19 and 20 (72%), and 2-(dimethylphenyl)-propiophenones 21 and 22 (68%), respectively (Scheme 2). In the case of the secondary alcohol 2 mainly products derived from hydration at the C(6), C(9) double bond are formed, namely the mixture of diols 23 and 24 (21%), and the mixture of the isomeric 2-(dimethylphenyl)propanals 25, 26 and 27 (3%) (Scheme 3). - The structures of 12–14, 19/20, 21/22, 23/24 and 25/26/27 were established by spectroscopic data. In the case of 12 and 13 the degradation of their mixture to the known 1-(dimethylphenyl)ethanols 17/18 confirmed the assignment. - The most probable mechanism for the rearrangement of 3 is shown in Schemes 4 and 5. The reaction proceeds from 3 through a, b and g to 12 and 13; 14 is formed via e, f and i . In the case of 4 and 6 only the reaction analogue to 3 → a → b → g ?12/13 takes place. The isomeric aldehyds 25–27 formed from 2 could have the structures s, t , and v . The former two could be generated in a similar way as 12/13 from 3 , the latter one as shown in Scheme 8.     

Reduction and methyl transfer kinetics of the alpha subunit from acetyl coenzyme a synthase

Stopped-flow was used to evaluate the methylation and reduction kinetics of the isolated alpha subunit of acetyl-Coenzyme A synthase from Moorella thermoacetica. This catalytically active subunit contains a novel Ni-X-Fe4S4 cluster and a putative unidentified n = 2 redox site called D. The D-site must be reduced for a methyl group to transfer from a corrinoid-iron-sulfur protein, a key step in the catalytic synthesis of acetyl-CoA. The Fe4S4 component of this cluster is also redox active, raising the possibility that it is the D-site or a portion thereof. Results presented demonstrate that the D-site reduces far faster than the Fe4S4 component, effectively eliminating this possibility. Rather, this component may alter catalytically important properties of the Ni center. The D-site is reduced through a pathway that probably does not involve the Fe4S4 component of this active-site cluster.     

The synthesis of functionalized cis'-bicyclo ¦3.3.0¦octanes

A number of polyfunctionalized cis-bicycio ¦3.3.0¦octanes have been synthesized starting from the tricyclic key intermediate $\text{5}$ which was obtained by the intramolecular cyclopropanation reaction of the diazo keto ester $\text{4}$. Selected stereocontrolled transformations of $\text{5}$ using nucleophiles and electrophiles have been studied for the preparation of the title compounds.     

The addition of methyllithium to 2,2,4,4-tetramethylcyclobutan-1-one-3-thione. The generation and capture of a bishomoenolate anion.

Methyllithium added to 2,2,4,4-tetramethylcyclobutan-1-one-3-thione to produce lithium 3-methylthio-2,2,4,4-tetramethylbicyclo[1.1.0]but-1-oxide. This bishomoenolate was alkylated on carbon by methyl iodide, but retained the bicyclo[1.1.0]butane skeleton when silated with chlorotrimethylsilane. The ease of oxidation of a series of 1,3-diheteroatom substituted bicyclo[1.1.0]butanes was determined.     

Inactivation of nitroalkane oxidase upon mutation of the active site base and rescue with a deprotonated substrate

Mutation of Asp402 in nitroalkane oxidase to Asn or Ala inactivates the enzyme with neutral nitroethane as substrate, but the activity can be rescued with the nitroethane anion. The V/K values of the D402N and D402A enzymes with the nitroethane anion are independent of pH, whereas the V/K values of the wild-type and D402E enzymes are pH dependent with both the protonated and the deprotonated forms of nitroethane. Moreover, although the V/K value of the D402E enzyme with neutral nitroethane is 20-fold less than that of the wild-type enzyme, there is only a 2-fold difference in the V/K values with the nitroethane anion. These results are fully consistent with a primary role for Asp402 as the active site base in nitroalkane oxidase which abstracts the substrate alpha-proton.