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.     

Retardation in two-atom systems

We consider the old problem of two identical two-level atoms a fixed distance r apart, one excited at t = 0, the other unexcited, and the field in the vacuum state. We are interested specifically in the higher order retardation effects, which have not previously been discussed. We show the existence of an unexpected interference term in the probability for atom 1 to be excited which sets in two retardation times after atom 1 begins to decay.     

Comment on Cole and Zou's Classical Computations of the Hydrogen Ground State

The interesting results of stochastic-electrodynamical computations of the hydrogen ground state suggest other numerical experiments that might sharpen our understanding of the differences between classical and quantum theory.     

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.     

Radiation reaction and the nonrelativistic theory of the electron

Radiation reaction must be included in the nonrelativistic Heisenberg equation of motion of the point electron in order to preserve the position-momentum commutation rule.     

Casimir-Lifshitz theory and metamaterials

Based on a generalization of the Lifshiftz theory, we calculate Casimir forces involving magnetodielectric and possibly anisotropic metamaterials, focusing on the possibility of repulsive forces. It is found that Casimir repulsion decreases with magnetic dissipation, and even a small Drude background in metallic-based metamaterials acts to make attractive a Casimir force that would otherwise be predicted to be repulsive. The sign of the force also depends sensitively on the degree of optical anisotropy of the metamaterial and on the form of the frequency dependency of the magnetic response.