Efficient and practical synthesis of modular chiral beta-organochalcogeno amines, ArYCH2CH(R)NH2, and single crystal structures of (S) - MsOCH2CH(Bz)NH3+ center dot Cl- and (R)-MsOCH2CH(Ph)NH3+ center dot Cl-

Modular chiral I3-organochalcogeno amines, ArYCH2CH(R)NH2 (4a-4g) where R = Me, Bz, Ph; and ArY = PhS, BzSe and 4-MeOC6H4Te respectively have been synthesized and characterized. Compounds 4a-4g were synthesized (Method II) from chiral aminoalkyl 13-methanesulfonate hydrochlorides, MsOCH2CH(R)NH3+ center dot Cl- (2a-2c) through nucleophilic displacement of MsO- with organochalcogenolate (ArY-). In another attempt (Method I) chiral beta-organotelluro amines (4a-4c) were prepared by deprotection of chiral N-boc I3-organotelluro amides, 4-MeOC6H4TeCH2CH(R)NH-Boc (3a-3c), which in turn, 13,-,1 were made from chiral N-boc 13-methanesulfonate amides (la-lc) and ArTeNa. 1H, and FTIR spectra of all the compounds (3a-3c and 4a-4g) were characteristic. The composition of 3a-3c was determined by elemental analysis. The a]TD values of 3b-3c and 4a-4g were determined. The single crystal structures of (S)-2b and (R)-2c were determined by X-Ray diffraction studies. Both (S)-2b and (R)2c were crystallized in orthorhombic system and the Flack parameter x was found 0.08(12) and 0.00(2) respectively. The crystal of (S)-2b contain two asymmetric units with gauche (A) and staggered (B) conformations. There are NH Cl-, NH-O and CH-O intra and intermolecular secondary interactions in (S)-2b and (R)-2c resulting in supramolecular structures. (C) 2015 Elsevier By. All rights reserved.

Pd-Catalyzed Hydroborylation of Alkynes: A Ligand Controlled Regioselectivity Switch for the Synthesis of alpha- or beta-Vinylboronates

A ligand controlled selective hydroborylation of alkynes to alpha- or beta-vinylboronates has been developed using a Pd catalyst. The high alpha-selectivity displayed by this reaction can be switched to furnish beta-vinylboronates by altering the ligand from a trialkylphosphine to N-heterocyclic carbene. A variety of terminal alkynes are shown to furnish the corresponding alpha- or beta-vinylboronates in good to excellent selectivity and yield. The mechanistic studies suggest that the solvent is the proton source and bromobenzene functions as an important additive in driving this reaction forward.

Pd-Catalyzed Hydroborylation of Alkynes: A Ligand Controlled Regioselectivity Switch for the Synthesis of alpha- or beta-Vinylboronates

A ligand controlled selective hydroborylation of alkynes to alpha- or beta-vinylboronates has been developed using a Pd catalyst. The high alpha-selectivity displayed by this reaction can be switched to furnish beta-vinylboronates by altering the ligand from a trialkylphosphine to N-heterocyclic carbene. A variety of terminal alkynes are shown to furnish the corresponding alpha- or beta-vinylboronates in good to excellent selectivity and yield. The mechanistic studies suggest that the solvent is the proton source and bromobenzene functions as an important additive in driving this reaction forward.

Short-Time Beta Relaxation in Glass-Forming Liquids Is Cooperative in Nature

Temporal relaxation of density fluctuations in supercooled liquids near the glass transition occurs in multiple steps. Using molecular dynamics simulations for three model glass-forming liquids, we show that the short-time beta relaxation is cooperative in nature. Using finite-size scaling analysis, we extract a growing length scale associated with beta relaxation from the observed dependence of the beta relaxation time on the system size. We find, in qualitative agreement with the prediction of the inhomogeneous mode coupling theory, that the temperature dependence of this length scale is the same as that of the length scale that describes the spatial heterogeneity of local dynamics in the long-time alpha-relaxation regime.

On variant distribution and coarsening behavior of the a phase in a metastable beta titanium alloy

The stereology, variant distribution and coarsening behavior of semicoherent alpha(hcp) precipitates in a beta(bcc) matrix of a Ti5553 alloy has been analyzed, and a dominant 3-variant cluster has been observed in which the variants are related to each other by an axis-angle pair <<11(2)over bar> 0 >/60 degrees. Shape and spatial distribution independent elastic self and interaction energies for all pairwise and triplet combinations of a have been calculated and it is found that the 3-cluster combination that is experimentally observed most frequently has the lowest energy for the semicoherent state. The coarsening behavior of the delta distribution follows LSW kinetics after an initial transient, and has been modeled by phase field methods. (C) 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

The effect of alloy composition on instabilities in the beta phase of titanium alloys

A metastable nano-scale disordered precipitate with orthorhombic symmetry has been identified using high resolution scanning transmission electron microscopy. The phase, termed O', is metastable, formed by a shuffle mechanism involving a {110}<1<(1)over bar>0> transverse phonon wave in samples of Ti-26Nb-2Zr (at.%) quenched from the beta phase. The addition of 2% Zr to Ti-26Nb appears to suppress significantly the stability of both the {11 (2) over bar}<111> shear and 2/3 <111> longitudinal phonon wave but promotes the {110}<1<(1)over bar>0> transverse shuffle. This results in the nano-size O' phase being homogeneously formed in the parent beta phase matrix rather than the massive alpha `' phase. (C) 2016 Elsevier B.V. All rights reserved.

A nano-scale instability in the beta phase of dilute Ti-Mo alloys

A nano-scale instability in the beta phase resulting in the formation of the disordered orthorhombic O' phase has been discovered in a fairly dilute binary Ti-Mo alloy, using selected area electron diffraction and high resolution scanning transmission electron microscopy. The O' phase informed in the alloy when the Mo content exceeds a critical value. The instability occurs in beta-solutionized samples that have been quenched to room temperature and is found to co-exist with athermal omega to phase. Interestingly, this nano-scale instability, involving the {110}<1<(1)over bar>0> soft-phonon shuffle, occurs in the beta phase without deliberate additions of either interstitial or substitutional solutes. (C) 2016 Elsevier Ltd. All rights reserved.