Conjugate reactions: New potentials of an old idea

Main concepts of the Shilov–Ostwald theory of conjugate chemical reactions are analyzed from the standpoint of complex reaction kinetics, theory of reaction routes, and thermodynamics of irreversible processes. Classification of conjugate reactions and an algorithm of catalytic system design for conducting these processes are proposed.     

Synthesis and characterization of 2-substituted bornane pharmacophores for novel cannabinergic ligands

Analogously to the fenchyl and adamantyl groups, the bornyl and epimeric isobornyl groups are compact lipophilic substituents that can be incorporated into drug design to improve pharmacological or physicochemical properties. Methods are reported for the synthesis and characterization of 2-substituted norbornanes and bornanes that can serve as novel cannabinergic ligand intermediates.     

A novel synthesis of functionalized tetrahydrofurans by an Oxa-Michael/Michael cyclization of gamma-hydroxyenones

An approach to highly functionalized tetrahydrofuran derivatives based upon a novel Oxa-Michael/Michael dimerization of cis-gamma-hydroxyenones is presented. The reaction begins with either 1,2-dioxines or trans-gamma-hydroxyenones and proceeds by addition of one molecule of trans-gamma-hydroxyenone to another molecule of cis- or trans-gamma-hydroxyenone catalyzed by an alkoxide or hydroxide base. Subsequent intramolecular Michael addition of the keto-enolate gives the observed tetrahydrofurans. Substitution at both the 2- and 4-positions of the gamma-hydroxyenone is tolerated; however, for 4-substituted gamma-hydroxyenones, selectivity issues arise due to the possibility of heterochiral or homochiral dimerizations. The major products were those with all contiguous groups trans.     

A novel synthesis of tolunitriles by selective ammoxidation

A new approach to synthesize tolunitriles is reported. Tolunitriles can be prepared by selective ammoxidation of methylbenzyl chlorides prepared by chloromethylation of toluene. The total yields can reach 83% and the selectivity of tolunitriles is almost 100%. This approach provides a new path for preparing alkylbenzonitriles and other aromatic nitriles.     

A novel pyrrole synthesis

The silver(I)-promoted oxidative cyclization of homopropargylamines at room temperature provides a novel access to pyrroles. Homopropargylamines are readily available by the addition of a propargyl Grignard reagent to Schiff bases.     

Differentiation of diastereomeric bornane derivatives by 13C NMR spectroscopy

Three diastereomeric bornane derivatives have been assigned configurational structures by ¹³C NMR measurements in the presence of Yb(dpm)₃.     

铟促进的烯丙基硒醚的合成

烯丙基溴和炔丙基溴在铟促进下与二硒化合物反应，生成烯丙基和炔丙基硒醚。反应无需严格的无水无氧条件，烯丙基溴以α-位与二硒化合物反应，产率55%～91%。     

A novel synthesis of perfluoroalkylglycine

Perfluoroalkylglycine was obtained through perfluoroalkylation of 2-phenyl-5-etho-xyoxazole using RFI-Na2S2O4 reagent system, followed by acid hydrolysis of the intermediates, 2-phenyl-4-perfluoroalkyl-5-ethoxyoxazole and 2-phenyl-4-perfluoroalkyl-2-oxazolin-5-one.     

A novel synthesis of tetramesityldisilene

Dimesityldiclorosilane undergoes reductive coupling with potassium-graphite to afford a mixture of cyclic polysilanes in a high yield and purity; this mixture is quantitatively converted to the title compound by photochemical irradiation.     

A novel synthesis of pyrromethenones

Pyrromethenones are prepared by a process involving acylation of an N-aminopyrrole with a suitable acetylenic acid,followed by sequential 5-exo-dig cyclization and 3,5-sigmatropic shift.     

A novel three-component butenolide synthesis

[reaction: see text]. 5-Acylamino butenolides can be assembled by a multicomponent reaction (MCR) of isocyanides, glyoxals, and acetophosphonic acid diethylesters, followed by a intramolecular Wittig-type reaction. The reaction can be performed either in one pot or with the isolation of the intermediate Passerini product. This versatile reaction offers three independent inputs displayed in the final product. Applications in combinatorial chemistry and natural product synthesis can be envisioned.     

A novel synthesis of Aporhoeadanes

A one-pot synthesis of aporhoeadanes from the reaction of 3,4-dihydro-isoquinolines, 2-chloromethylbenzoyl chloride and sodium hydroxide, is described.     

A novel synthesis of diaminomethanes

Diaminomethanes have been synthesized by reaction of 1,3-benzodioxole and 1,3-benzoxathiole with a double amount of sodium dialkyl and alkyl aryl amides.     

Nanoscale biocoordination polymers: novel materials from an old topic

Nature bestows many gifts upon us, among which countless biomolecules have the ability to bridge metal ions and exert the important function in biology. By taking advantage of specific interactions between metal ions and biomolecules, this article highlights a novel concept for construction of nanoscale biocoordination polymers through replacement of synthetic organic molecules with natural biomolecules as building blocks. The most recent advances are summarized and future challenges are discussed. It can be anticipated that nanoscale biocoordination polymers will become a diverse and rapidly growing class of novel materials and potentially lead to a breakthrough in biological applications.     

A novel synthesis of nitroform by the nitrolysis of cucurbituril

Cucurbituril has a high symmetry and rigid structure. When cucurbit[6]uril (CB[6]) was nitrolyzed with the mixed solution of acetic anhydride in fuming nitric acid, nitroform (NF) was generated. NF also can be obtained by the nitration of both CB[5,7,8]. This nitration procedure provides a lower risk, inexpensive, new preparation of nitroform, and the reaction condition of this new method is very mild.