Chiral synthons from campholenaldehyde: enantiospecific synthesis of diquinane and linear triquinanes

Enantiospecific syntheses of diquinane and linear triquinanes were accomplished, starting from the readily available alpha-campholenaldehyde employing a Nazarov reaction as the key step. (C) 2010 Elsevier Ltd. All rights reserved.

Chiral gels derived from secondary ammonium salts of (1R, 3S)-(+)-camphoric acid

In order to have access to chiral gels, a series of salts derived from (1R, 3S)-(+)-camphoric acid and various secondary amines were prepared based on supramolecular synthon rationale. Out of seven salts prepared, two showed moderate gelation abilities. The gels were characterized by differential scanning calorimetry, table top rheology, scanning electron microscopy, single crystal and powder X-ray diffraction. Structure property correlation based on X-ray diffraction techniques remain inconclusive indicating that some of the integrated part associated with the gelation phenomena requires a better understanding.

Anatase-rutile transformation in Fe/TiO2, Th/TiO2 and Cu/TiO2 catalysts and its possible role in metal-support interaction

Based on in-situ Mossbauer and X-ray diffraction studies, it is shown that in the Fe/TiO2 catalyst, the anatase-rutile transformation of the TiO2 support is facilitated by the Fe2+ ions formed during the reduction. The transformation occurs at lower temperatures in Th/TiO2 and Cu/TiO2 compared to pure TiO2. In general, the transformation of anatase to rutile seems to occur at or below the temperature (approximately 770 K) at which strong-metal-support-interaction manifests itself.

Polymorphism in a TADDOL analogue induced by the presence of a chiral impurity

Crystallization of a TADDOL analogue results in an orthorhombic P2(1)2(1)2(1) form while the presence of a minute amount of a chiral impurity in the crystallization is found to be responsible for crystallization in a monoclinic P2(1) form.

A regio and stereospecific radical annulation route to chiral tricyclo[4.3.1.o3,7]decane (isotwistane) system1 synthesis of (+)-10-α-Naphthyl-5-epi-Pupukean-9-one

Contrary to that of phenyl derivative 1 the radical 4 adds to radicophiles in an inter- followed by intra-molecular radical Michael addition (radical annulation), furnishing a novel route to chiral isotwistanes 5.

Diastereoisomeric (η6-arene)ruthenium(II) chiral Schiff base complexes: crystal structure of a triphenylphosphine adduct

Reaction of [(eta-6-p-cymene)RuCl(L star)] with AgClO4 in Me2CO gives a perchlorate complex which on subsequent treatment with PPh3, gamma-picoline or Cl- yields adducts showing that there can be retention as well as inversion of configuration at the metal centre. The (R)Ru,(S)C absolute configurations of the chiral centres in the triphenylphosphine adduct have been established by an X-ray diffraction study [HL star, (S)-alpha-methylbenzylsalicylaldimine]. The CD spectral study reveals that there is an inversion of configuration during formation of the PPh3 adduct.

Structural synthesis by transformation of binary chains Strukturelle synthese durch umwandlung binaerer ketten

The paper presents a general method of structural synthesis which can be used to derive all possible simple- and multiple-jointed chains of positive, zero or negative degree-of-freedom. In this method all possible chains with N links and F degrees-of-freedom are derived by the transformation of the corresponding “binary chains” with N binary links and F degrees-of-freedom. The method is illustrated by applying to the case of chains with degrees-of-freedom 1,2,0 and −1.

A real transformation for modal analysis of flexible damped spacecraft

Modal approach is widely used for the analysis of dynamics of flexible structures. However, space analysts yet lack an intimate modal analysis of current spacecraft which are rich with flexibility and possess both structural and discrete damping. Mathematical modeling of such spacecraft incapacitates the existing real transformation procedure, for it cannot include discrete damping, demands uncomputable inversion of a modal matrix inaccessible due to its overwhelming size and does not permit truncation. On the other hand, complex transformation techniques entail more computational time and cannot handle structural damping. This paper presents a real transformation strategy which averts inversion of the associated real transformation matrix, allows truncation and accommodates both forms of damping simultaneously. This is accomplished by establishing a key relation between the real transformation matrix and its adjoint. The relation permits truncation of the matrices and leads to uncoupled pairs of coupled first order equations which contain a number of adjoint eigenvectors. Finally these pairs are solved to obtain a literal modal response of forced gyroscopic damped flexibile systems at arbitrary initial conditions.

A Vicarious One-Pot Transformation of a Fluorocyclitol to a Polycyclitol: Observation of a Formal 4-Fold Axial-Equatorial Epimerization on a Conformationally Locked Scaffold

A conformationally locked fluoropentol undergoes an interesting transformation to (trans,anti,trans,anti,trans)-perhydro-2,3,4a,6,7,8a-naphthalenehexol essentially under conditions of base-induced transesterification. The proposed rationale for the observed metamorphosis involves a nucleophilic displacement of fluoride, and subsequent stereo- and regioselective anti-Furst-Plattner-type ring-opening of the epoxide thus formed.

An in situ electron microscope investigation of the icosahedral-to-decagonal quasicrystalline transformation in Al-20 at.% Mn

The solid-state transformation behaviour of the icosahedral phase in rapidly solidified Al-20 at.% Mn has been investigated by in situ heating experiments in the transmission electron microscope. As-rapidly-solidified Al-20 at.% Mn consists mainly of a dendritic icosahedral phase, with a small amount of interdendritic f.c.c. agr-Al. During subsequent heat treatment at temperatures below about 500°C, the dendritic icosahedral phase grows and consumes the interdendritic agr-Al. At about 500°C the decagonal phase nucleates near icosahedral dendrite and grain boundaries and then grows into the icosahedral matrix by lateral motion of ledges 10-20 nm high across facet planes normal to the twofold symmetry axes. At about 600°C the decagonal phase transforms into a crystalline phase. The present study suggests that solid-state decomposition of the icosahedral phase is the mechanism of decagonal phase formation in as-rapidly-solidified Al-Mn alloys.

Bile-Acids in Asymmetric-Synthesis.2. Cholic-Acid Derived Novel Chiral Auxiliaries For Asymmetric Diels-Alder Reactions

Cholic acid-based chiral acrylate 5 yields a Diels-Alder adduct with cyclopent