Catalytic Enantioselective Reaction of α‐Phenylthioacetonitriles with Imines Using Chiral Bis(imidazoline)–Palladium Catalysts

The catalytic enantioselective reaction of α‐phenylthioacetonitriles with imines has been developed. The reaction of various imines proceeds in good yields and diastereo‐ and enantioselectivities in the presence of chiral bis(imidazoline)–palladium catalysts. The obtained products can be converted into β‐aminonitrile or β‐aminoamide compounds without loss of enantiopurity.     

Ruthenium‐Immobilized Periodic Mesoporous Organosilica: Synthesis,Characterization, and Catalytic Application for Selective Oxidation of Alkanes

Periodic mesoporous organosilica (PMO) is a unique material that has a crystal‐like wall structure with coordination sites for metal complexes. A Ru complex, [RuCl₂(CO)₃]₂, is successfully immobilized onto 2,2’‐bipyridine (BPy) units of PMO to form a single‐site catalyst, which has been confirmed by various physicochemical analyses. Using NaClO as an oxidant, the Ru‐immobilized PMO oxidizes the tertiary C?H bonds of adamantane to the corresponding alcohols at 57 times faster than the secondary C?H bonds, thereby exhibiting remarkably high regioselectivity. Moreover, the catalyst converts cis‐decalin to cis‐9‐decalol in a 63 % yield with complete retention of the substrate stereochemistry. The Ru catalyst can be separated by simple filtration and reused without loss of the original activity and selectivity for the oxidation reactions.     

Native Mannose‐Dominant Extraction by Pyridine–Phenol Alternating Oligomers Having an Extremely Efficient Repeating Motif of Hydrogen‐Bonding Acceptors and Donors

Pyridine–phenol alternating oligomers in which pyridine and phenol moieties are alternatingly linked through acetylene bonds at the 2,6‐positions of the aromatic rings were designed and synthesized. The pyridine nitrogen atom and the neighboring phenolic hydroxyl group were oriented so that they do not form an intramolecular hydrogen bond but cooperatively act as hydrogen‐bonding acceptor and donor in a push–pull fashion for the hydroxyl group of saccharides. The longer oligomer strongly bound to lipophilic glycosides in 1,2‐dichloroethane, and association constants approached 10⁸ M ^?1. Moreover, the oligomer extracted native saccharides from a solid phase to apolar organic solvents up to the extent of an equal amount of the oligomer and showed mannose‐dominant extraction among naturally abundant hexoses. The oligomer bound to native saccharides even in 20 % DMSO‐containing 1,2‐dichloroethane and exhibited association constants of greater than 10 M ^?1 for D ‐mannose and D ‐glucose.     

Versatile In Situ Generated N‐Boc‐Imines: Application to Phase‐Transfer‐Catalyzed Asymmetric Mannich‐Type Reactions

The efficient construction of nitrogen‐containing organic compounds is a major challenge in chemical synthesis. Imines are one of the most important classes of electrophiles for this transformation. However, both the available imines and applicable nucleophiles for them are quite limited given the existing preparative methods. Described herein are imine precursors which generate reactive imines with a wide variety of substituents under mild basic conditions. This approach enables the construction of various nitrogen‐containing molecules which cannot be accessed by the traditional approach. The utility of the novel imine precursor was demonstrated in the asymmetric Mannich‐type reaction under phase‐transfer conditions.     

10‐Step Asymmetric Total Synthesis and Stereochemical Elucidation of (+)‐Dragmacidin D

The asymmetric synthesis of dragmacidin D ( 1 ) was completed in 10 steps. Its sole stereocenter was set by using direct asymmetric alkylation enabled by a C₂‐symmetric tetramine and lithium N‐(trimethylsilyl)‐tert‐butylamide as the enolization reagent. A central Larock indole synthesis was employed in a convergent assembly of the heterocyclic subunits. The stereochemical evidence from this work strongly supports the predicted S configuration at the 6′′′ position, which is consistent with other members of the dragmacidin family of natural products.     

A bar impact tester for dynamic fracture testing of ceramics and ceramic composites

A bar impact test was developed to study the dynamic fracture responses of precracked ceramic bars, Al₂O₃ and 15/29-percent volume SiC_w/Al₂O₃. Crack-opening displacement was measured with a laser-interferometric displacement gage and was used to determine the crack velocity and the dynamic stress-intensity factorK _I ^dyn . The crack velocity andK _I ^dyn increased with increasing impact velocity while the dynamic-initiation fracture toughness,K _Id, did not vary consistently with increasing impact velocities.Paper was presented at the 1992 SEM Spring Conference on Experimental Mechanics held in Las Vegas on June 8–11.     

Shear Failure of Inconel 718 under Dynamic Loads

Kinetics of deformation and fracture of nickel–iron alloy Inconel 718 under dynamic shear loading was measured using a split torsional Hopkinson bar facility and high-speed photography. Tubular specimens with a reduced gage length and a starter notch were sheared at strain rates up to 6 × 10³ s⁻¹. High-speed photographs of fiducial lines scribed on the specimen surface showed the development of local strains and cracking. This paper describes the experimental and analytical procedures, illustrates average and local plastic strain evolution, and presents shear crack initiation times and propagation speeds.     

Further studies on dynamic crack branching

The newly derived dynamic-crack-branching criterion with its modifications is verified by the dynamicphotoelastic results of dynamic crack branchings in thinpolycarbonate, single-edged crack-tension specimens. Successful crack branching was observed in four specimens and unsuccessful branching in another. Crack branching consistently occurred when the necessary conditions ofK _I =K _{I b} =3.3 MPa \(\sqrt m\) and the sufficiency condition ofr _o =r _c =0.75 mm were satisfied simultaneously. In the unsuccessful branching test, the necessary condition was not satisfied sinceK _I was always less thanK _{I b} .     

A New Flexible Multibody Beam Element Based on the Absolute Nodal Coordinate Formulation Using the Global Shape Function and the Analytical Mode Shape Function

Several techniques for the reduced dimensionality of finite elementformulations were considered as component mode reduction methods in themiddle sixties. These techniques are widely used in flexiblemultibody simulations for solving small deformation problems. Theabsolute nodal coordinate formulation for solving large rotation anddeformation problems has been established as a full finite elementmethod instead of using similar kinds of reduction techniques. In thispaper, a reduced order absolute nodal coordinate formulation is newlyestablished by introducing the global beam shape function and theanalytical deformation modes as a full finite element. This formulationleads to a constant and symmetric mass matrix as the conventionalabsolute nodal coordinate formulation, and makes it possible to reducethe number of elements and system coordinates of the beam structurewhich undergoes large rotations and large deformations. Numericalexamples show that the excellent agreements between thepresent formulation and the conventional absolute nodal coordinateformulation using a large number of elements are examined. These results demonstratethat the present formulation has high accuracy in the sense that thepresent solutions are similar to the conventional ones with fewersystem coordinates, and high efficiency in computation.     

Asymptotic Behavior of Solutions of the Compressible Navier-Stokes Equations on the Half Space

Asymptotic behavior of solutions of the compressible Navier-Stokes equations on the half space R ⁿ₊(n≥2) is considered around a given constant equilibrium. A solution formula for the linearized problem is derived, and L^p estimates for solutions of the linearized problem are obtained for 2≤p≤∞. It is shown that, as in the case of the Cauchy problem, the leading part of the solution of the linearized problem is decomposed into two parts, one that behaves like diffusion waves and the other one purely diffusively. There, however, are some aspects different from the Cauchy problem, especially in considering spatial derivatives. It is also shown that the solution of the linearized problem approaches for large times the solution of the nonstationary Stokes problem in some L^p spaces; and, as a result, a solution formula for the nonstationary Stokes problem is obtained. Large-time behavior of solutions of the nonlinear problem is then investigated in L^p spaces for 2≤p≤∞ by applying the results on the linearized analysis and the weighted energy method. The results indicate that there may be some nonlinear interaction phenomena not appearing in the Cauchy problem.