Novel Selectivity in Carbohydrate Reactions III. Selective Deprotection of p-Methoxybenzyl (PMBn) Ethers of Carbohydrates by Tin(IV)Chloride 1

In multi-step syntheses involving polyhydroxylated natural products such as carbohydrates that are variously derivatized at different positions, orthogonal removal of one or another type of protecting group is of vital importance. Discrimination of different classes of protecting groups, such as ethers, esters, etc., is often possible with a great degree of success, as for example, selective removal of an 0-acetyl by catalytic transesterification in the presence of an ether protecting group, or hydrogenolytic removal of a benzyl ether protection in the presence of ester groups such as acetates.³ Differentiation of different types of protecting groups within a given class of protecting groups has also been similarly achieved with great success, as for example, hydrogenolytic removal of a benzyl ether group in the presence of a methyl ether.³ However, the situation becomes more challenging when the same protecting group is used to mask more than one position in a polyfunctional molecule and their preferential partial deprotection is required. Selective unmaslung of one or more of such protecting groups has been achieved in some cases.4 Of particular interest to us was the regioselective deprotection of the 2-0-benzyl group of per- 0-benzylated 1,6-anhydromannopyranose mediated by SnC14 (1) and Tic14 (2). Considering the greater susceptibility of p-methoxybenzyl (PMBn) ethers to Lewis acid catalysts5 and the complexation of benzyl ethers with 14b and 24b16 we decided to investigate the action of 1 on PMBn ethers of some carbohydrates, We expected the methoxy substituent on the phenyl group in the PMBn moiety to enhance complexation with 1, possibly resulting in a facile reaction under mild conditions. Since 1 is a strong Lewis acid, the need to use chlorotrimethylsilane and anisole, as in the tin(I1)chloride- chlorotrimethylsilane-anisole system for deprotection of PMBn ethers, can be eliminated. Moreover, the complex formation in the case of 1 presents possibilities for unusual regioselectivity in partial de-0-p-methoxybenzylation reactions, a problem that has not been addressed in reports on the oxidative cleavage of PMBn ethers by 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ)⁷ ceric ammonium nitrate (CAN),⁸ N-bromosuccinimide (NBS)⁸ or bromine⁸.

     

Synthetic Studies on Sialoglycoconjugates 104: Synthesis of Kdn-Lewis X Ganglioside Analogs Containing Modified Reducing Terminal and L-Rhamnose in Place of L-Fucose 1 2

Abstract

KDN-Le^x ganglioside analogs (10, 13, 16 and 19) containing the modified reducing terminal and L-rhamnose in place of L-fucose have been synthesized. Glycosidation of methyl 2,3,4-tri-O-benzyl-1-thio-α-L-rhamnopyranoside (1) with 2-(trimethylsilyl)ethyl O-(2-acetamido-4,6-O-benzylidene-2-deoxy-β-D-glucopyranosyl)-(1→3)-O-(2,4,6-tri-O-benzyl-α-D-galacopyranoside (2), followed by reductive ring opening of the benzylidene acetal, gave 2-(trimethylsilyl)ethyl O-(2,3,4-tri-O-benzyl-α-L-rhamnopyranosyl)-(1→3)-O-(2-acet-amido-6-O-benzyl-2-deoxy-β-D-glucopyranosyl)-(1→3)-O-(2,4,6-tri-O-benzyl-β-D-galactopyranosyl)-(1→4)-2,3,6-tri-O-benzyl-β-D-glucopyranoside (4). The tetrasaccharide 4 was coupled with methyl O-(methyl 4,5,7,8,9-penta-O-acetyl-3-deoxy-D-glycero-α-D-galacto-2-nonulopyranosylonate)-(2→3)-2,4,6-tri-O-benzoyl-1-thio-β-D-galactopyranoside(5), using dimethyl(methylthio)sulfonium triflate (DMTST), to give the hexasaccharide 6, which was converted into compound 11 in the usual manner. Compounds 8 and 11 were transformed, via bromination of the reducing terminal, radical reduction, O-deacylation and saponification of the methyl ester, into the desired KDN-Le^x hexasaccharides (10, 13). On the other hand, glycosylation of 2-(tetradecyl)hexadecanol with α-trichloroacetimidates 14 and 17, afforded the target ganglioside analogs 16 and 19.

     

Phase-Measuring Algorithms to Suppress Spatially Nonuniform Phase Modulation in a Two-Beam Interferometer

Phase modulation of presently used phase-shifting interferometers is assumed to be spatially uniform across the observing aperture. However, calibration errors or the configuration of an interferometer can cause a spatial nonuniformity in the phase modulation. Spatial nonuniformity causes a significant error in the measured phase when the phase modulator has nonlinear sensitivity. An even-order nonlinearity in the phase modulation in particular contributes to the errors. Lowest-order errors can be suppressed by adding a new symmetry to the sampling functions of the phase-shifting algorithm, however the algorithm suffers from large random noise. The random noise is shown to be decreased substantially by applying one more sampled frame to the algorithm. We derive new seven-sample and eight-sample algorithms that can compensate for a nonuniform phase shift and has much less random noise than the previous algorithm we proposed.     

Transport,thermal, and magnetic properties in heavy-fermion superconductor Ce2CoIn8

We have grown high purity single crystals of Ce₂CoIn₈ using the self-flux technique, and have investigated its transport, thermal, and magnetic properties, including the anisotropic features. Single crystals of Ce₂CoIn₈ were grown in the lower temperature region to avoid the formation of un-wanted phases such as CeCoIn₅ and CeIn₃ impurities. The results of the structural and physical measurements imply that the present single crystals have high purity. The electrical resistivity and specific heat measurements demonstrate that Ce₂CoIn₈ has a superconducting ground state with a distinct non-Fermi liquid character. This indicates that the superconductivity in Ce₂CoIn₈ arises out of the verge of the underlying quantum critical instability mediated by the antiferromagnetic correlations. Additionally, we investigate the crystalline electric field (CEF) energy scheme based on the temperature dependence of the specific heat and the anisotropic features in the susceptibility. We propose one of the CEF level schemes calculated on the basis of the CEF model that the first and second CEF states are located at Δ₁ = 82 K and Δ₂ = 102 K above the ground state doublet, respectively.     

Shape optimization of a body located in incompressible flow using adjoint method and partial control algorithm

The purpose of this study is to obtain an optimal shape of a body located in an incompressible viscous flow. The optimal shape of the body is defined so as to minimize the fluid forces acting on it by determining the surface coordinates based on the finite element method and the optimal control theory. The performance function, which is used to judge the optimality of a shape, is defined as the square sum of the drag and lift forces. The minimization problem is solved using an adjoint equation method. The gradient in the adjoint equation is affected by the finite element configuration. The use of a finite element mesh whose shape is appropriate for the procedure is important in shape optimization. If the finite element mesh used is not suitable for computations, the exact gradient is not calculated. Therefore, a structured mesh is used for the adjacent area of the body and all finite element meshes are refined using the Delaunay triangulation at each iteration computation. The weighted gradient method is applied as the minimization technique. Using an algorithm in which all nodal coordinates on the surface of the body are employed and starting from a circle as an initial shape, a front‐edged and rear‐round shape is obtained because of the vortices at the back of the body. To overcome this difficulty, we introduced the partial control algorithm, in which some of the nodal coordinates on the surface of the body are updated. From four cases of computational studies, we reveal that the optimal shape has both sharp front and sharp rear edges. All computations are conducted at Reynolds number Re=250. The minimum value of the performance function is obtained. Copyright © 2010 John Wiley & Sons, Ltd.