Aspartyl methyl ester formation via aspartimide ring opening: a proposed modification of the protocols used in Boc- and Fmoc-based solid-phase peptide synthesis

Aspartimide formation is still an unresolved problem in the solid-phase peptide synthesis of aspartic acid-containing peptides, following either Boc- or Fmoc-based synthetic strategies. α-Aspartyl peptides of high purity can be obtained, despite aspartimide formation, by incorporating an additional step in the Boc- and Fmoc-based solid-phase peptide synthesis protocols, consisting of treatment of the peptide-resin with methanol in the presence of 2% DIEA (v/v) for 15 min immediately after completion of the peptide chain elongation.     

Binary electrocatalysts for organic oxidations

The electro-oxidation of formaldehyde and methanol has been studied on a number of binary platinum electrocatalysts. These comprised mixed electro-deposits of Pt with Sb, As, Bi, Hg, Re, Te or Sn and a range of homogeneous Pt-Rh alloys of different, known, surface composition. These systems were found to exhibit an enhanced activity over that of platinum alone, and this behaviour was correlated with the ease of adsorption of oxygen on the added metal. The activities for organic oxidation were compared with predictions of a model involving reaction between adsorbed oxygen and organic species on the metal surface. The proposed mechanism accounts for the behaviour of both homogeneous and heterogeneous alloy systems.     

Stereoselective synthesis of cis and trans-fused 3a-aryloctahydroindoles using cyclization of N-vinylic α-(methylthio)acetamides: synthesis of (−)-mesembrane

Treatment of N-(2-arylcyclohex-1-en-1-yl)-α-(methylthio)acetamides with N-chlorosuccinimide (NCS) gave 3a-aryl-2,3,3a,4,5,6-hexahydro-3-(methylthio)indol-2-ones. Desulfurization of the cyclization products followed by a catalytic hydrogenation of the resulting hexahydroindol-2-ones gave predominantly or exclusively trans-fused octahydroindol-2-ones. On the other hand, reduction of the desulfurization products with Et₃SiH in CF₃CO₂H exclusively provided cis-fused octahydroindol-2-ones. A chiral induction of N-[2-(3,4-dimethoxy)phenylcyclohex-1-en-1-yl]-α-(methylthio)acetamide having an (R)-1-(1-naphthyl)ethyl group on the nitrogen atom led to the synthesis of (−)-mesembrane and (−)-trans-mesembrane.     

Selective reduction of alkenes, α,β-unsaturated carbonyl compounds, nitroarenes, nitroso compounds, N,N-hydrogenolysis of azo and hydrazo functions as well as simultaneous hydrodehalogenation and reduction of substituted aryl halides over PdMCM-41 catalyst under transfer hydrogen conditions

Chemoselective reductions of alkenes, α,β-unsaturated carbonyl compounds, nitro and nitroso compounds, N,N-hydrogenolysis of azo and hydrazo functions as well as simultaneous reduction and hydrodehalogenation of substituted aryl halides, including bulkier substrates, were achieved by catalytic transfer hydrogenation (CTH) using mesoporous PdMCM-41 catalyst. The yields were practically unaffected upon recycling of the catalyst. Further, the CTH process is accomplished without affecting the reduction of any other reducible functional group.     

Synthesis of the substituted spiro segment of halichlorine--use of radical cyclization and stereospecific cuprate addition to an α,β-unsaturated lactam

Radical cyclization (26a,b → 27a,b+28) and cuprate addition (28 → 31) were used as key steps to construct the spiro core 4 of halichlorine.     

α-Hydroxy carboxylic acids as ligands for enantioselective diethylzinc additions to aromatic and aliphatic aldehydes

The first examples of the enantioselective titanium-mediated diethylzinc additions to aromatic and aliphatic aldehydes catalyzed by optically active α-hydroxy acids are presented. The reactions proceed with very good yield and good asymmetric induction. Enantioselectivities up to 90% are obtained depending on ligand and aldehyde used. A stereochemical model for the reaction is proposed.     

卵磷脂有序体中碳酸钙超微颗粒的研究

近些年来，国内外对超微颗粒的研究正处方兴未艾，由于纳米级材料与大块物质的特性截然不同，引起了国内外科学工作者的关注，试图用各种方法制备各种超微颗粒．在有序体中制备铂、佬、金、银、锅等超微颗粒已有文献介绍山，在表面活性剂AOT与水形成的有序体中制各碳酸钙超细颗粒也有报导问，用脂质体合成某些超微颗粒的工作也有文章发表［3］．但是由卵磷脂（PC）与水组成人。膜体系制备碳酸钙超微颗粒尚未见到报导．我们根据分子有序组合体具有”隔室化”作用，形成纳米级空间的思路，采用PC－H。0有序体系作为生成碳酸钙的反应场所．…     

Towards peptide versions of Cram's host-guest chemistry: the synthesis of C-disubstituted glycines with binaphthol-based crowned side-chains

Dietherification of the hydroxy groups of various α,α-disubstituted α-amino acids or their precursors, possessing either an achiral frame derived from α-hydroxymethylserine, or a 2,2′,6,6′-tetrasubstituted biphenyl frame with only an axial chirality, or a frame with α-carbon chirality derived from α-methyl-(L)-DOPA, using (R)-2,2′-bis-(5-tosyloxy-3-oxa-1-pentyloxy)-1,1′-binaphthyl as alkylating agent, gave a new series of amino acids bearing binaphthol-based crown-ethers, as building blocks for the construction of short-chain peptide helices with topologically well-localized receptors.     

A facile synthetic method of α-quaternary-β,γ-unsaturated aldehydes via the stereoselective 1,4-elimination and α-regioselective Ferrier reaction

The 1,4-elimination reaction of 2-substituted-(2Z)-4-methoxy-O-alkenyl acetals with n-butyllithium is shown to afford the 2-substituted-(1Z,3E)-O-1,3-dienyl acetals in high stereoselectivities. The Ferrier reaction of the O-1,3-dienyl acetals thus obtained provides the corresponding α-quaternary-β,γ-unsaturated aldehydes in excellent yields with high α-regioselectivities.     

Original synthesis of α-chloroketones in azaheterocyclic series using TDAE approach

We report herein an original and rapid synthesis of new α-chloroketones in azaheterocyclic series based on TDAE strategy from the reaction between 2-(trichloromethyl)quinoxaline and aromatic aldehydes. This reactivity has been generalized to a quinolinic trichloride.