Improved Synthesis of C2-Symmetrical Pyridinediols and Synthesis of Cs-Symmetrical Pyridinediols

Base-induced reaction of 2,6-dimethylpyridine (2,6-lutidine) (1) with two equivalents of various ketones has been reported to provide C2-symmetrical pyridine diols 3. Closer examination reveals that competitive di-addition to a single methyl group can occur providing Cs-symmetrical pyridine diols 7. By varying the lithiation times, the formation of this side product could be maximized or minimized on the basis of a mechanistic proposal for the competing pathways. The formation of the Cs-diol 7 could be excluded completely by using potassium diisopropylamide as base; high yields of C2-symmetrical pyridine diols 3 are obtained. Regioselective additions of 1 to (R)-fenchone and (-)-menthone were also achieved.

Attrition-enhanced total resolution leads to homochiral families of amino acid derivatives

The total resolution of five structurally similar racemizable amino acid derivatives, three of which have racemic crystal structures, was performed simultaneously. By enantioselective incorporation in an amino acid derivative that forms a conglomerate the other four were deracemized on attrition-induced grinding. The outcome of the resolution was random (R) or (S), but all compounds had the same absolute configuration and high enantiomeric purities.

Acid Catalyzed Ring-opening Reactions of Optically Pure 2-Aryl-3,3-dimethyloxetanes

Some ring-opening reactions of optically pure 2-aryl-3,3-dimethyl oxetanes have been examined under strongly protic or Lewis acid conditions. Ring-opening occurred at the benzylic position and partial inversion of configuration was observed in the case of hydrolysis or alcoholysis of the optically pure oxetanes catalyzed by H2SO4. The acid concentration affects the degree of inversion of configuration in water or methanol. On reaction with n-butyllithium or lithium thiolates aided by Lewis acid (BF3.ether) the corresponding β-substituted benzyl alcohols were obtained. Substitution now occurs at the least hindered carbon and the configuration of the asymmetric center remains unaffected

Practical Aspects of Carbon-Carbon Cross-Coupling Reactions Using Heteroarenes

The use of cross-coupling reactions for the preparation of alkylated and arylated heteroaromatic compounds has increased tremendously over the past two decades. This has been driven on the one hand by the increasingly complex structures of new drugs, most of which contain one or more heterocyclic motifs. On the other hand, the development of new catalysts and reaction conditions for these reactions has rendered even the most unreactive of heteroarenes amenable to cross-coupling chemistry. Not only have new bulky electron-donating ligands been created that allow the coupling of aryl chlorides under mild conditions, but also the use of ligand-free palladium, in particular at very low doses, sometimes called homeopathic palladium, has served to bring down the cost of these reactions. More recent and enabling developments are the use of catalysts based on cheap metals such as nickel, copper, and iron. Scale-up issues are availability and cost of starting materials, cost of the catalysts (related to cost of the metal and the ligand, intrinsic activity and stability of the catalyst), solvent choice, and removal of the metal t

Beaver Ponds: Resurgent Nitrogen Sinks for Rural Watersheds in the Northeastern United States

Beaver-created ponds and dams, on the rise in the northeastern United States, reshape headwater stream networks from extensive, free-flowing reaches to complexes of ponds, wetlands, and connecting streams. We examined seasonal and annual rates of nitrate transformations in three beaver ponds in Rhode Island under enriched nitrate-nitrogen (N) conditions through the use of 15N mass balance techniques on soil core mesocosm incubations. We recovered approximately 93% of the nitrate N from our mesocosm incubations. Of the added nitrate N, 22 to 39% was transformed during the course of the incubation. Denitrification had the highest rates of transformation (97–236 mg N m−2 d−1), followed by assimilation into the organic soil N pool (41–93 mg N m−2 d−1) and ammonium generation (11–14 mg N m−2 d−1). Our denitrification rates exceeded those in several studies of freshwater ponds and wetlands; however, rates in those ecosystems may have been limited by low concentrations of nitrate. Assuming a density of 0.7 beaver ponds km−2 of catchment area, we estimated that in nitrate-enriched watersheds, beaver pond denitrification can remove approximately 50 to 450 kg nitrate N km−2 catchment area. In rural watersheds of southern New England with high N loading (i.e., 1000 kg km−2), denitrification from beaver ponds may remove 5 to 45% of watershed nitrate N loading. Beaver ponds represent a relatively new and substantial sink for watershed N if current beaver populations persist