Stereoselective inverse conjugate addition of nitrogen and carbon nucleophiles to allenyl phosphine oxide. Synthesis of α,β-unsaturated phosphine oxides

Issue in Honor of Prof. Paweł Kafarski

Hydrazides and hydrazones as versatile Michael-Donors for iminium-catalyzed conjugate addition reactions

396 : il., graf.

The development of an asymmetric palladium-catalyzed conjugate addition and its application toward the total syntheses of taiwaniaquinoid natural products

The asymmetric synthesis of quaternary stereocenters remains a challenging problem in organic synthesis. Past work from the Stoltz laboratory has resulted in methodology to install quaternary stereocenters α- or γ- to carbonyl compounds. Thus, the asymmetric synthesis of β-quaternary stereocenters was a desirable objective, and was accomplished by engineering the palladium-catalyzed addition of arylmetal organometallic reagents to α,β-unsaturated conjugate acceptors.

Herein, we described the rational design of a palladium-catalyzed conjugate addition reactions utilizing a catalyst derived from palladium(II) trifluoroacetate and pyridinooxazole ligands. This reaction is highly tolerant of protic solvents and oxygen atmosphere, making it a practical and operationally simple reaction. The mild conditions facilitate a remarkably high functional group tolerance, including carbonyls, halogens, and fluorinated functional groups. Furthermore, the reaction catalyzed conjugate additions with high enantioselectivity with conjugate acceptors of 5-, 6-, and 7-membered ring sizes. Extension of the methodology toward the asymmetric synthesis of flavanone products is presented, as well.

A computational and experimental investigation into the reaction mechanism provided a stereochemical model for enantioinduction, whereby the α-methylene protons adjacent the enone carbonyl clashes with the tert-butyl groups of the chiral ligand. Additionally, it was found that the addition of water and ammonium hexafluorophosphate significantly increases the reaction rate without sacrificing enantioselectivity. The synergistic effects of these additives allowed for the reaction to proceed at a lower temperature, and thus facilitated expansion of the substrate scope to sensitive functional groups such as protic amides and aryl bromides. Investigations into a scale-up synthesis of the chiral ligand (S)-tert-butylPyOx are also presented. This three-step synthetic route allowed for synthesis of the target compound of greater than 10 g scale.

Finally, the application of the newly developed conjugate addition reaction toward the synthesis of the taiwaniaquinoid class of terpenoid natural products is discussed. The conjugate addition reaction formed the key benzylic quaternary stereocenter in high enantioselectivity, joining together the majority of the carbons in the taiwaniaquinoid scaffold. Efforts toward the synthesis of the B-ring are presented.

Measurement of small vibration amplitudes of a rough surface by an interferometer with a self-pumped phase-conjugate mirror

The application of a Michelson interferometer with a self-pumped phase-conjugate mirror to measure small vibration amplitudes of a rough surface is described. The distorted wave front of the light that is diffusely reflected from the rough surface is restored by phase conjugation to provide an interference signal with a high signal-to-noise ratio. The vibration amplitudes of a stainless-steel sample are measured with a precision of similar to 5 nm. (C) 2000 Optical Society of America OCIS codes: 120.3180, 190.5040, 120.7280.

The conjugate representation of signal envelope

The problem of the representation of signal envelope is treated, motivated by the classical Hilbert representation in which the envelope is represented in terms of the received signal and its Hilbert transform. It is shown that the Hilbert representation is the proper one if the received signal is strictly bandlimited but that some other filter is more appropriate in the bandunlimited case. A specific alternative filter, the conjugate filter, is proposed and the overall envelope estimation error is evaluated to show that for a specific received signal power spectral density the proposed filter yields a lower envelope error than the Hilbert filter.

LES and hybrid LES/RANS simulations for conjugate heat transfer over a matrix of cubes

Large Eddy Simulation (LES) and a novel k -l based hybrid LES/RANS approach have been applied to simulate a conjugate heat transfer problem involving flow over a matrix of surface mounted cubes. In order to assess the capability and reliability of the newly developed k -l based hybrid LES/RANS, numerical results are compared with new LES and existing RANS results. Comparisons include mean velocity profiles, Reynolds stresses and conjugate heat transfer. As well as for hybrid LES/RANS validation purposes, the LES results are used to gain insights into the complex flow physics and heat transfer mechanisms. Numerical simulations show that the hybrid LES/RANS approach is effective. Mean and instantaneous fluid temperatures adjacent to the cube surface are found to strongly correlate with flow structure. Although the LES captures more mean velocity field complexities, broadly time averaged wake temperature fields are found similar for the LES and hybrid LES/RANS. Copyright © 2005 by the American Institute of Aeronautics and Astronautics, Inc. All rights reserved.

Generation of conjugate meshes for complex geometries for coupled multi-physics simulations

Over recent years we have developed and published research aimed at producing a meshing, geometry editing and simulation system capable of handling large scale, real world applications and implemented in an end-to-end parallel, scalable manner. The particular focus of this paper is the extension of this meshing system to include conjugate meshes for multi-physics simulations. Two contrasting applications are presented: export of a body-conformal mesh to drive a commercial, third-party simulation system; and direct use of the cut-Cartesian octree mesh with a single, integrated, close-coupled multi-physics simulation system. Copyright © 2010 by W.N.Dawes.

Simultaneous determination of microcystin-LR and its glutathione conjugate in fish tissues by liquid chromatography-tandem mass spectrometry

A sensitive and selective liquid chromatography-tandem mass spectrometry method was developed and validated for the simultaneous quantitative determination of microcystin-LR (MC-LR) and its glutathione conjugate (MC-LR-GSH) in fish tissues. The analytes were extracted from fish liver and kidney using 0.01 M EDTA-Na-2-5% acetic acid, followed by a solid-phase extraction (SPE) on Oasis HLB and silica cartridges. High-performance liquid chromatography (HPLC) with electrospray ionization mass spectrometry, operating in selected reaction monitoring (SRM) mode, was used to quantify MC-LR and its glutathione conjugate in fish liver and kidney. Recoveries of analytes were assessed at three concentrations (0.2, 1.0, and 5 mu g g(-1) dry weight [DW]) and ranged from 91 to 103% for MC-LR, and from 65.0 to 75.7% for MC-LR-GSH. The assay was linear within the range from 0.02 to 5.0 mu g g(-1) DW, with a limit of quantification (LOQ) of 0.02 mu g g(-1) DW. The limit of detection (LOD) of the method was 0.007 mu g g(-1) DW in both fish liver and kidney. The overall precision was determined on three different days. The values for within- and between-day precision in liver and kidney were within 15%. This method was applied to the identification and quantification of MC-LR and its glutathione conjugate in liver and kidney of fish with acute exposure of MC-LR. (c) 2007 Elsevier B.V. All rights reserved.

Real-time non-destructive testing of dynamic holograms in doubly-doped LiNbO3 crystals using phase-conjugate technique

Nankai University