Palladium-catalyzed amidation of enol triflates: a new synthesis of enamides

[reaction: see text] The palladium-catalyzed coupling of a range of enol triflates with amides, carbamates, and sulfonamides has been developed. This offers a simple and widely applicable synthesis of enamides, which may not be readily available by other means.     

Derivation of the General Case Sagnac Result Using Non-Time-Orthogonal Analysis

The Sagnac time delay and fringe shift dependency on angular velocity and enclosed area are derived from the rotating reference frame using non-time-orthogonal (NTO) tensor analysis. NTO analysis differs from traditional approaches by postulating that the continuous and single valued nature of physical time constrains simultaneity in a rotating frame to be unique (and thus not a matter of convention.) This implies anisotropy in the physical, local speed of light and invalidity of the hypothesis of locality for NTO frames. The Sagnac relationship for the most general case, in which the area enclosed is not circular and does not have the axis of rotation passing through its center, is determined.     

New Perspectives on the Relativistically Rotating Disk and Non-Time-Orthogonal Reference Frames

The rotating disk problem is analyzed on the premise that proper interpretation of experimental evidence leads to the conclusion that the postulates upon which relativity theory is based, particularly the invariance of the speed of light, are not applicable to rotating frames. Different postulates based on the Sagnac experiment are proposed, and from these postulates a new relativistic theory of rotating frames is developed following steps similar to those initially followed by Einstein for rectilinear motion. The resulting theory agrees with all experiments, resolves problems with the traditional approach to the rotating disk, and exhibits both traditionally relativistic and non-relativistic characteristics. Of particular note, no Lorentz contraction exists on the rotating disk circumference, and the disk surface, contrary to the assertions of Einstein and others, is found to be Riemann flat. The variable speed of light found in the Sagnac experiment is then shown to be characteristic of non-time-orthogonal reference frames, of which the rotating frame is one. In addition, the widely accepted postulate for the equivalence of inertial and non-inertial standard rods with zero relative velocity, used liberally in prior rotating disk analyses, is shown to be invalid for such frames. Further, the new theory stands alone in correctly predicting what was heretofore considered a spurious non-null effect on the order of 10^–13 found by Brillet and Hall in the most accurate Michelson-Morley type test to date. The presentation is simple and pedagogic in order to make it accessible to the non-specialist.     

pH Dependence of the Au-CN Species Adsorbed onto Activated Carbon — Comments

In a recent paper by McGrath et al. [Hyp. Interact. 139/140 (2002), 471] the authors appear to have overlooked a body of prior work on the aurocyanide activated carbon system based on X-ray photoelectron spectroscopy. Unlike Mössbauer spectroscopy, limited to chemical state interpretations for a single absorber, XPS is usually capable or both quantitative chemical state assignment and stoichiometry for most atoms within the system. This earlier work shows that rather than producing a mixture of Au(CN) ₂ ^? and AuCN the effect of acid on the aurocyanide adsorbed on activated carbon is to actually produce limited chain length oligomers such as the tetramer Au₄(CN) ₅ ^? . It clearly demonstrates the evolution of bridging (N_b) and terminal (N_t) nitrogen atoms with the relative concentration (for both N?:?Au and N_b?:?N_t) terminating at a stoichiometric ratio indicative of the oligomer. Other shortcomings of the paper in question are discussed.     

Über die Eigenschaften des α-Metaxylylhydrazins und seine Einwirkung auf Acetessigester

Ohne Zusammenfassung     

A dual-catalysis/anion-binding approach to the kinetic resolution of allylic amines

A dual-catalysis approach enables the small-molecule catalyzed kinetic resolution of allylic amines by acylation. By employing 2 mol % of each 4-(pyrrolidino)pyridine (PPY) and a readily available chiral hydrogen-bonding cocatalyst, the first nonenzymatic kinetic resolution of allylic amines was accomplished with s factors of up to 20.     

Relativistic Rotation: A Comparison of Theories

Alternative theories of relativistic rotation considered viable as of 2004 are compared in the light of experiments reported in 2005. En route, the contentious issue of simultaneity choice in rotation is resolved by showing that only one simultaneity choice, the one possessing continuous time, gives rise, via the general relativistic equation of motion, to the correct Newtonian limit Coriolis acceleration. In addition, the widely dispersed argument purporting Lorentz contraction in rotation and the concomitant curved surface of a rotating disk is analyzed and argued to be lacking for more than one reason. It is posited that not by theoretical arguments, but only via experiment can we know whether such effect exists in rotation or not. The Coriolis/simultaneity correlation, and the results of the 2005 experiments, support the Selleri theory as being closest to the truth, though it is incomplete in a more general applicability sense, because it does not provide a global metric. Two alternatives, a modified Klauber approach and a Selleri–Klauber hybrid, are presented which are consistent with recent experiment and have a global metric, thereby making them applicable to rotation problems of all types.     

N-sulfonyloxy carbamates as reoxidants for the tethered aminohydroxylation reaction

The use of N-sulfonyloxy carbamates as reoxidants for the tethered aminohydroxylation (TA) reaction is reported. These new conditions obviate the requirement for lithium hydroxide and tBuOCl in the oxidation mixture. In addition to providing aminohydroxylation products in good yields, the catalyst loadings can be reduced to just 1 mol % osmium. Moreover, for the first time, homoallylic alcohols are now viable substrates for the TA reaction.     

Comments on “the chemisorption and decomposition of no on the (110) surface of iridium” by D.E. Ibbotson,T.S. Wittrig and W.H. Weinberg

In a recent paper by Ibbotson et al. [Surface Sci. 110 (1981) 294] the chemisorption of NO on Ir(110) was studied with Hel UV photoelectron spectroscopy, amongst other techniques. For molecular adsorption, the levels observed at 13.5, 10.4 and 8.5 eV below the Fermi level were associated with the 4σ, 5σ and 1π orbitais of NO, respectively. It is proposed that such a specific assignment is not possible, rather that the observed levels are due to photoemission from (5$\text{}\text{?}$gs + 1g?p). Some other errors in the literature regarding the assignment problem are also discussed.     

Analysis of the Anomalous Brillet and Hall Experimental Result

The persistent, second-order, anomalous signal found in the Brillet and Hall experiment is derived by applying 4D differential geometry in the rotating earth frame. By incorporating the off diagonal time-space components of the rotating frame metric directly into the analysis, rather than arbitrarily transforming them away, one finds a signal dependence on the surface speed of the earth due to rotation about its axis. This leads to a Brillet-Hall signal prediction in remarkably close agreement with experiment. No signal is predicted from the speed of the earth in solar or galactic orbit, as the associated metric for gravitational orbit has no off diagonal component. To corroborate this result, a repetition by other experimentalists of the Brillet-Hall experiment, in which the test apparatus turns with respect to the earth surface, is urged.