Triene Cyclizations. The Total Synthesis of Pallescensin A

The total synthesis of pallescensin A has been achieved using a six π, thermal electrocyclization reaction as the key step.     

Anisotropic α decay

A microscopic approach to the problem of anisotropic α decay in deformed nuclei is presented. Nuclear wave functions are calculated within the BCS approach, and the WKB semiclassical approximation is used for the penetration through the deformed Coulomb barrier. Results are compared with recent experimental data obtained at CERN by the ISOLDE and NICOLE collaborations. The predictions of the model for well-deformed nuclei are in very good agreement with experimental findings.     

Combining the benefits of homogeneous and heterogeneous catalysis with tunable solvents and nearcritical water

The greatest advantage of heterogeneous catalysis is the ease of separation, while the disadvantages are often limited activity and selectivity. We report solvents that use tunable phase behavior to achieve homogeneous catalysis with ease of separation. Tunable solvents are homogeneous mixtures of water or polyethylene glycol with organics such as acetonitrile, dioxane, and THF that can be used for homogeneously catalyzed reactions. Modest pressures of a soluble gas, generally CO?, achieve facile post-reaction heterogeneous separation of products from the catalyst. Examples shown here are rhodium-catalyzed hydroformylation of 1-octene and p-methylstyrene and palladium catalyzed C-O coupling to produce o-tolyl-3,5-xylyl ether and 3,5-di-tert-butylphenol. Both were successfully carried out in homogeneous tunable solvents followed by separation efficiencies of up to 99% with CO? pressures of 3 MPa. Further examples in tunable solvents are enzyme catalyzed reactions such as kinetic resolution of rac-1-phenylethyl acetate and hydrolysis of 2-phenylethyl acetate (2PEA) to 2-phenylethanol (2PE). Another tunable solvent is nearcritical water (NCW), whose unique properties offer advantages for developing sustainable alternatives to traditional processes. Some examples discussed are Friedel-Crafts alkylation and acylation, hydrolysis of benzoate esters, and water-catalyzed deprotection of N-Boc-protected amine compounds.     

A General Synthesis of 2-Phenylselenenylenones. The Reaction of Unsaturated Ketones with a Phenylselenenyl Chloride/Pyridine Complex

The generation of specific enolates via Michael addition of nucleophiles to unsaturated ketones has proven to be an extremely useful process in organic synthesis. With regard to this we felt that the incorporation of a phenylselenenyl group in the 2-position of an enone would (a) enhance the ability of the enone to undergo Michael addition, (b) provide, after Michael addition, a stabilized enolate for the subsequent introduction of a substituent in the 2-position and (c) allow for the eventual introduction of a new double bond via the well-known selenoxide β-elimination reaction.¹ While a few 2-phenylselenenylenones have been previously reported in the literature,² no general method currently exists for their preparation.³ We now wish to report a general method for the synthesis of these systems in good yield under extremely mild reaction conditions. In future communications we will demonstrate the versatility of this class of compounds in a variety of enone mono- and dialkylation reactions.     

Universal Sets of n Points for One-bend Drawings of Planar Graphs with n Vertices

This paper shows that any planar graph with n vertices can be point-set embedded with at most one bend per edge on a universal set of n points in the plane. An implication of this result is that any number of planar graphs admit a simultaneous embedding without mapping with at most one bend per edge.     

Preparation and reactivity of α-phenylselenenyl ethers

α-Phenylsclenenyl cyclic ethers may be prepared by the reactions of either lactols or lactol acetates with benzeneselenol, or from lactones by the “one-pot” process of reduction and Lewis acid catalyzed selenation. The tetrahydropyranyl phenyl selenides also exhibit a significant anomeric effect and its size has been estimated. The selenenyl ethers are converted to enol ethers through an oxidative elimination process, and an exploration of their reactivity toward amide bases and lithium alkyls has been made.     

Absolute alpha-decay width of212Po in a mixed shell-and-cluster model

We have reproduced the absolute width of theα decay of the ground state of²¹²Po in a model in which the shell model is combined with a²⁰⁸Pb+α cluster model, and found that the amount of core+α clustering in the parent state is ～30%.     

Probing nuclear surfaces by heavy ion reactions

An analysis of the recently measured ¹⁶O + ²⁶Mg one- and two-proton transfer reaction is given. It is shown that these reactions probe progressively deeper regions of the surface of the two colliding nuclei.     

Clusters as Many-Body Resonances

A formalism to evaluate the resonant states produced by two particles moving outside a closed shell core is presented. The two-particle states are calculated by using a single-particle representation consisting of bound states, Gamow resonances and scattering states in the complex energy plane (Berggren representation). Two representative cases are analysed corresponding to whether the Fermi level is below or above the continuum threshold. It is found that long-lived resonances are mostly determined by either bound states or by narrow Gamow resonances. However, they are significantly affected by wide resonances and the continuum background itself.