Reactions of sulfoxonium allylides with nitrile oxides and ring transformations of their reaction products

Reactions of allylides ($\text{1}$) with nitrile oxides ($\text{2}$) afforded furanylglyoxylate oxime ($\text{3}$) and 6H-l,2-oxazine ($\text{4}$). Ring transformations of $\text{3}$ and $\text{4}$ gave $\text{4}$ and pyrrolinone ($\text{6}$), respectively.     

Pyrolysis reaction of carpronium chloride and its structurally related compounds. 2—a mass spectrometric study of the lactonization mechanism

The mechanism of the pyrolysis reaction of carpronium chloride [(CH₃)₃N⁺? (CH₂)₃? COOCH₃CI^?] leading to γ-butyrolactone and tetramethylammonium chloride was investigated by means of thermal analysis, pyrolysis gas chromatography mass spectrometry and field desorption mass spectrometry, using deuterium labelling. The results indicated that carpronium chloride pyrolysed to yield equimolar amounts of γ-butyrolactone and tetramethylammonium chloride, methyl transfer occurred between N and O during the pyrolysis process. The mechanism is discussed on the basis of the experimental results, and with the aid of the theoretical results calculated by the CNDO/2 method. The mechanism presented is as follows. γ-Butyrolactone is formed by the intramolecular migration of the π-orbital of C?O to the carbon adjacent to [(CH₃)₃N]⁺ via a 5-membered ring transition state, accompanied by a bimolecular reaction between [(CH₃)₃N]⁺ and the CH₃ of O? CH₃, resulting in the formation of tetramethylammonium chloride in an amount equimolar with γ-butyrolactone.     

Mass spectrometric studies on gibberellins

Based on the element maps of twenty-two gibberellin methyl esters fragmentations are discussed, which are characteristic of the common structural features as well as structural modification in gibberellin homologues.     

Synthesis of (3′R,5′S)-3′-hydroxycotinine using 1,3-dipolar cycloaddition of a nitrone

To synthesize (3′R,5′S)-3′-hydroxycotinine [(+)-1], the main metabolite of nicotine (2), cycloaddition of C-(3-pyridyl)nitrones 3a, 3c, and 15 with (2R)- and (2S)-N-(acryloyl)bornane-10,2-sultam [(2R)- and (2S)-8] was examined. Among them, l-gulose-derived nitrone 15 underwent stereoselective cycloaddition with (2S)-8 to afford cycloadduct 16, which was elaborated to (+)-1.     

Spin-probe ESR study on the dynamics of liquid molecules in the MCM-41 nanochannel: temperature dependence on 2-propanol and water

A spin-probe ESR study has been made on the dynamics of 2-propanol and water molecules in the nanochannel of MCM-41 at various temperatures. In the former system, 2-propanol is separated into two phases: one with molecules immobilized in the ESR time scale and the other with mobile ones, even at temperatures more than 40 degrees higher than the bulk melting point. In the case of water, on the other hand, only the "immobilized" water was detected at a temperature as high as 313 K. At higher temperature, spin-probe molecule undergoes anisotropic rotational diffusion to reduce resistance from the solvent molecules in the nanochannel. These results are explained in relation to the intermolecular network intensified in the nanochannel. Static as well as dynamic structures of these solutions have been discussed.     

Synthesis of end‐functionalized polyethers by phosphazene base‐catalyzed ring‐opening polymerization of 1,2‐butylene oxide and glycidyl ether

For the living ring‐opening polymerization (ROP) of epoxy monomers, the catalytic activity of organic superbases, tert‐butylimino‐tris(dimethylamino)phosphorane, 1‐tert‐butyl‐2,2,4,4,4‐pentakis(dimethylamino)‐2Λ⁵,4Λ⁵‐catenadi(phosphazene), 2,8,9‐triisobutyl‐2,5,8,9‐tetraaza‐1‐phosphabicyclo[3.3.3]undecane, and 1‐tert‐butyl‐4,4,4‐tris(dimethylamino)‐2,2‐bis[tris(dimethylamino)phosphoranylidenamino]‐2Λ⁵,4Λ⁵‐catenadi(phosphazene) (t‐Bu‐P₄), was confirmed. Among these superbases, only t‐Bu‐P₄ showed catalytic activity for the ROP of 1,2‐butylene oxide (BO) to afford poly(1,2‐butylene oxide) (PBO) with predicted molecular weight and narrow molecular weight distribution. The results of the kinetic, post‐polymerization experiments, and MALDI‐TOF MS measurement revealed that the t‐Bu‐P₄‐catalyzed ROP of BO proceeded in a living manner in which the alcohol acted as the initiator. This alcohol/t‐Bu‐P₄ system was applicable to the glycidol derivatives, such as benzyl glycidyl ether (BnGE) and t‐butyl glycidyl ether, to afford well‐defined protected polyglycidols. The α‐functionalized polyethers could be obtained using different functionalized initiators, such as 4‐vinylbenzyl alcohol, 5‐hexen‐1‐ol, and 6‐azide‐1‐hexanol. In addition, the well‐defined cyclic‐PBO and PBnGE were successfully synthesized using the combination of t‐Bu‐P₄‐catalyzed ROP and click cyclization. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Measuring grain rotation at the nanoscale

In this paper, we introduced a method to measure grain rotation of nanomaterials under external stress using a high pressure diamond anvil cell and the Laue microdiffraction technique at a synchrotron facility. We used tungsten carbide marker crystals to investigate grain rotation activities of 3 and 500?nm nickel media. Our results show that the grain rotation of 3 and 500?nm nickel nanocrystals increase with pressure and finally rotation of 500?nm nickel tends to stop at a lower pressure/stress level than 3?nm nickel. 3?nm nickel nanocrystals show a higher rotation magnitude than 500?nm nickel nanocrystals. Our measurements show an effective method to study the grain rotation of nanomaterials especially in ultrafine nanocrystals.     

Effect of Protecting Groups and Solvents in Anomeric O-Alkylation of Mannopyranose1

Abstract

Anomeric O-alkylation of mannopyranoses with various protecting groups was investigated using mannose derivatives and 2,3-O-isopropylidene-l-O-trifluoro-methanesulfonyl-D-glycerol (1) as alkylating agent. Generally, in polar solvents higher α/β ratios were obtained than in nonpolar solvents. Sterically demanding protecting groups at the 6-O-position and polar solvents led to higher yields. Reactivity differences were explained by different complex formation. Based on these results mannopyranosyl-α(1-4) glucopyranosides 26 and 27 were synthesized using mannose derivatives 5 and 6 having a 6-O-(p-methoxyphenyl)diphenylmethyl group and galactosyl trifluoromethane-sulfonate 24 or nonafluorobutanesulfonate (nonaflate) 25, respectively, as alkylating agents.     

Synthetic Approach Toward the Partial Sequences of Betaglycan in the Linkage Region on Solid Support and in Solution Phase

We have synthesized, for the first time, the partial sequence of the betaglycan composed of the tetraosyl hexapeptide, which was directly usable as a probe for enzymatic glycosyl transfer. Stepwise elongation afforded the corresponding tetraosyl trichloroacetimidate. The common glycosyl dipeptide:[β‐d‐GlcA‐(1→3)‐β‐d‐Gal‐(1→3)‐β‐d‐Gal‐(1→4)‐β‐d‐Xyl‐(1→O)‐Ser‐Gly] was synthesized by glycosylation of the corresponding tetraosyl trichloroacetimidate and Ser‐Gly moiety. The glycosyl dipeptide was coupled with other core peptide parts in solution phase and on a solid support. These glycosyl hexapeptides were then transformed into the desired target compounds.