Bismuth compounds in organic synthesis. A one-pot synthesis of homoallyl ethers and homoallyl acetates from aldehydes catalyzed by bismuth triflate

[reaction: see text] Three one-pot methods for the conversion of aldehydes to homoallyl ethers catalyzed by Bi(OTf)(3).xH(2)O (1 < x < 4) have been developed. The one-pot synthesis of homoallyl ethers can be achieved either by in situ generation of the acetal followed by its reaction with allyltrialkylsilane or by a three-component synthesis in which the aldehyde, trimethylorthoformate or an alkoxytrimethylsilane and allyltrimethylsilane are mixed together in the presence of bismuth triflate (0.1-1.0 mol %). In addition, a three-component synthesis of homoallyl acetates, which is achieved by reacting the aldehyde, acetic anhydride, and allyltrimethylsilane in the presence of bismuth triflate (3.0-5.0 mol %), has been developed. The use of a relatively nontoxic, easy to handle, and inexpensive catalyst adds to the versatility of these methods.     

New chiral phosphine-phosphite ligands in the enantioselective palladium-catalyzed allylic alkylation

A series of chiral phosphine-phosphite ligands 1-6 have been synthesized and used in the enantioselective palladium-catalyzed reaction of rac-1,3-diphenyl-2-propenyl acetate with dimethyl malonate as nucleophile. Ligands 1a, 2, 3, 5a, 6a, and 6b have been synthesized starting from racemic tert-butylphenylphosphinoborane. The use of dynamically resolved Li phosphide (-)-sparteine provided the optically pure ligands. Crystals of the allylpalladium (6a) complex were obtained, suitable for X-ray crystal structure determination. The X-ray crystal structure of the allylpalladium (6a) complex revealed a longer palladium-carbon bond distance trans to the phosphine moiety indicating that the attack of the nucleophile takes place at the carbon trans to the phosphine moiety. This was confirmed by the fact that the phosphine moiety did not affect the enantioselectivity directly. Under mild reaction conditions, enantioselectivities up to 83% were obtained (25 degrees C) with ligand 1e. Systematic variation of the ligand bridge and the phosphite moiety showed that the configuration of the product is controlled by the atropisomerism of the biphenyl substituent at the phosphite moiety. The conformation of the biphenyl group, in turn, is controlled by the substituent at the chiral carbon in the bridge. Ligands with large bite angles yielded higher enantioselectivities.     

Aminosulf(ox)ides as ligands for Iridium(I)-catalyzed asymmetric transfer hydrogenation

A new class of efficient catalysts was developed for the asymmetric transfer hydrogenation of unsymmetrical ketones. A series of chiral N,S-chelates (6-22) was synthesized to serve as ligands in the iridium(I)-catalyzed reduction of ketones. Both formic acid and 2-propanol proved to be suitable as hydrogen donors. Sulfoxidation of an (R)-cysteine-based aminosulfide provided a diastereomeric ligand family containing a chiral sulfur atom. The two chiral centers of these ligands showed a clear effect of chiral cooperativity. In addition, aminosulfides containing two asymmetric carbon atoms in the backbone were synthesized. Both the sulfoxide-containing beta-amino alcohols and the aminosulfides derived from 1,2-disubstituted amino alcohols gave rise to high reaction rates and moderate to excellent enantioselectivities in the reduction of various ketones. The enantioselective outcome of the reaction was favorably affected by selecting the most appropriate hydrogen donor. Enantioselectivities of up to 97% were reached in the reduction of aryl-alkyl ketones.     

Fast-electron ejection from C,Ni, Ag and Au foils by <Superscript>36</Superscript><Emphasis Type="Italic">Ar</Emphasis><Superscript>18 + </Superscript> (95 MeV/u): Measurements of absolute cross-sections

Doubly differential electron velocity spectra induced by ³⁶Ar^{18 +} (95 MeV/u) from thin target foils (C, Ni, Ag, Au) were measured at GANIL (Caen, France) by means of the ARGOS multidetector and the time-of-flight technique. The main features observed in the forward spectra are convoy electrons, binary-encounter electrons, and (for the Au target only) a high-velocity tail which we attribute to a Fermi shuttle acceleration mechanism. Backward spectra do not show distinct structures. The spectra allow us to determine absolute singly differential cross-sections as a function of the target material and the emission angle. The convoy electron yield increases with the target atomic number, but for C their yield is so small that our experiment is not able to detect them. Absolute doubly differential cross-sections for binary-encounter electron ejection from C targets are well described by a transport theory which is based on the relativistic electron impact approximation (EIA) for electron production and which accounts for angular deflection, energy loss and energy straggling of the transmitted electrons.Received: 1 July 2003, Revised: 15 December 2003, Published online: 13 July 2004PACS: 34.50.Fa Electronic excitation and ionization of atoms (including beam-foil excitation and ionization) - 79.20.Rf Atomic, molecular, and ion beam impact and interactions with surfaces - 25.70.-z Low and intermediate energy heavy-ion reactions     

Search for high energy γ-rays emission in28Si,32S+64Ni dissipative reactions at about 5 MeV/amu incident energy

Photons emitted in the²⁸ Si+⁶⁴ Ni and³² S+⁶⁴ Ni reactions at 143 MeV and 156 MeV incident energy respectively, have been detected in coincidence with the ejected charged fragments. An array of 48 BaF₂ -rays detector and 6 solid state silicon detector telescopes have been used. Photon energy spectra measured in the energy range from 2 to 20 MeV in coincidence with ejectiles coming from deep inelastic reactions, are consistent with statistical emission from the reaction products.Thanks are due to Dr.T.Noorman for the suggestions in the statistical calculations and to Mr.C.Marchetta for the preparation of high quality targets.     

A Robust, Environmentally Benign Catalyst for Highly Selective Hydroformylation

By a sol-gel process a rhodium complex containing a diphosphane with a large natural P-Rh-P bite angle is covalently anchored in a silica matrix (see picture). The immobilized catalyst is a very selective hydroformylation catalyst that is completely and conveniently separated from the product and can be reused in numerous cycles.     

Synthesis of Cis- and Trans-1-methylcyclohexane-1,4-diols and Their 4-Hemisuccinate Esters

Stereoselective syntheses of the previously uncharacterized cis- and trans-1-methylcyclohexane-1,4-diols and their conversion to 4-hemisuccinate esters are described.     

Micro‐Raman analysis and finite‐element modeling of 3 C‐SiC microstructures

Micro‐ and nano‐electromechanical systems (MEMS and NEMS) fabricated in 3 C‐SiC are receiving particular attention thanks to the material physical properties: its wide band gap (2.3 eV), its ability to operate at high temperatures, its mechanical strength and its inertness to the exposure in corrosive environments. However, high residual stress (which is normally generated during the hetero‐epitaxial growth process) makes the use of 3 C‐SiC in Si‐based MEMS fabrication techniques very limited leading to a failure of micro‐machined/sensor structures. In this paper, micro‐Raman characterizations and finite‐element modeling (FEM) of microstructures realized on poly and single‐crystal (100) 3 C‐SiC/Si films are performed. Transverse optical (TO) Raman mode analysis reveals the stress relaxation on the free standing structure (796.5 cm⁻¹) respect to the stressed unreleased region (795.7 cm⁻¹). Also, microstructures as cantilever, bridge and planar rotating probe show an intense stress field located around the undercut region. Here, the TO Raman mode undergoes an intense shift, up to 2 cm⁻¹, ascribed to the modification of the Raman stress tensor. Indeed, the generalized axial regime, described by diagonal components of the Raman stress tensor, cannot be applied in this region. Raman maps analysis and FEM simulations show the ‘activation’ of the shear stress, i.e. non‐diagonal components of the stress tensor. The stress‐Raman modes shift correlation, in the case of fully non‐diagonal stress tensors, has been investigated. The aim of future works will be to minimize the stress field generation and the defects density within the epitaxial layer. Copyright © 2012 John Wiley & Sons, Ltd.