Lewis Base Catalysis of the Mukaiyama Directed Aldol Reaction: 40 Years of Inspiration and Advances

Since the landmark publications of the first directed aldol addition reaction in 1973, the site, diastereo‐, and enantioselective aldol reaction has been elevated to the rarefied status of being both a named and a strategy‐level reaction (the Mukaiyama directed aldol reaction). The importance of this reaction in the stereoselective synthesis of untold numbers of organic compounds, both natural and unnatural, cannot be overstated. However, its impact on the field extends beyond the impressive applications in synthesis. The directed aldol reaction has served as a fertile proving ground for new concepts and new methods for stereocontrol and catalysis. This Minireview provides a case history of how the challenges of merging site selectivity, diastereoselectivity, enantioselectivity, and catalysis into a unified reaction manifold stimulated the development of Lewis base catalyzed aldol addition reactions. The evolution of this process is chronicled from the authors’ laboratories as well as in those of Professor Teruaki Mukaiyama.     

Ion exchange chromatography coupled to inductively coupled plasma mass spectrometry for the study of Pt electro-dissolution

There is an ongoing debate regarding the mechanism of Pt electrochemical dissolution. However, only off-line methods have so far been used, where separation of Pt species is performed separately from their detection. In this study, ion exchange chromatography coupled to inductively coupled plasma mass spectrometry was used for the first time to separate and detect Pt species generated by the electro-dissolution of a Pt electrode in 0.5 M aqueous H₂SO₄ solution. Because these species are either neutral or cationic, they were converted to chloro-complexes using 0.1 M KCl to enable their separation by anion exchange chromatography. Chloro-aqua complexes were observed in addition to the two predominant species, namely PtCl₄²⁻ and PtCl₆²⁻. A good linear relationship was observed between the sum of peak areas for all complexes of a given Pt oxidation state and the Pt concentration, with a detection limit of 0.1 μg L⁻¹ being reached for Pt(II) and Pt(IV). Application of this speciation analysis method to real samples generated by potential cycling using cyclic voltammetry (CV) revealed that, in general, at least 80% of Pt was present as Pt(II), irrespectively of the cyclic potential range or of temperature (up to 60 °C). Still, quantitative spike recovery was achieved after adding known amounts of Pt(II) or Pt(IV) to a sample prepared by CV, which demonstrated that no significant species inter-conversion took place.     

Preparation of Nitriles by Dehydration of Primary Carboxawides with a Supported phosphorus pentoxide reagent

The use of a supported phosphorus pentoxide reagent in the synthesis of selected nitriles is discussed.     

A study of enthalpic relaxation of a liquid crystal

A liquid crystal, BL038, which was observed not to crystallize, has a glass transition at 215 K and a nematic to isotropic transition at 380 K. Samples aged below the glass transition at various temperatures T _a, exhibited an endotherm at the transition which developed with extent of ageing time, t _a. We attribute this endotherm to the relaxation of the glass towards the equilibrium liquid. The progress of the relaxation process was measured using differential scanning calorimetry. On subsequent reheating, the aged glass showed an apparent shift in the glass transition to higher temperatures. The endotherm was used to define the extent of enthalpic relaxation and the maximum value observed was found to increase initially then decrease, with the extent of undercooling from the glass transition temperature, Δ T, passing through a maximum for a Δ T = 15 K. From the temperature dependence of the relaxation times, an apparent activation enthalpy for the relaxation process of 85 ± 10 kJ mol^-1 was determined. The small value of the activation enthalpy compared with that found in the ageing of polymers reflects differences in the molecular species involved in relaxation processes.     

The Aqueous Ca2+ System,in Comparison with Zn2+, Fe3 +, and Al3 +: An Ab Initio Molecular Dynamics Study

Herein, we report on the structure and dynamics of the aqueous Ca²⁺ system studied by using ab initio molecular dynamics (AIMD) simulations. Our detailed study revealed the formation of well‐formed hydration shells with characteristics that were significantly different to those of bulk water. To facilitate a robust comparison with state‐of‐the‐art X‐ray absorption fine structure (XAFS) data, we employ a 1st principles MD‐XAFS procedure and directly compare simulated and experimental XAFS spectra. A comparison of the data for the aqueous Ca²⁺ system with those of the recently reported Zn²⁺, Fe³⁺, and Al³⁺ species showed that many of their structural characteristics correlated well with charge density on the cation. Some very important exceptions were found, which indicated a strong sensitivity of the solvent structure towards the cation′s valence electronic structure. Average dipole moments for the 2nd shell of all cations were suppressed relative to bulk water.     

Efficient algorithms for three‐dimensional axial and planar random assignment problems

Beautiful formulas are known for the expected cost of random two‐dimensional assignment problems, but in higher dimensions even the scaling is not known. In three dimensions and above, the problem has natural “Axial” and “Planar” versions, both of which are NP‐hard. For 3‐dimensional Axial random assignment instances of size n, the cost scales as Ω(1/ n), and a main result of the present paper is a linear‐time algorithm that, with high probability, finds a solution of cost O(n^–1+o(1)). For 3‐dimensional Planar assignment, the lower bound is Ω(n), and we give a new efficient matching‐based algorithm that with high probability returns a solution with cost O(n log n). © 2013 Wiley Periodicals, Inc. Random Struct. Alg., 46, 160–196, 2015     

Upper bound on the dark matter total annihilation cross section

We consider dark matter annihilation into standard model particles and show that the least detectable final states, namely, neutrinos, define an upper bound on the total cross section. Calculating the cosmic diffuse neutrino signal, and comparing it to the measured terrestrial atmospheric neutrino background, we derive a strong and general bound. This can be evaded if the annihilation products are dominantly new and truly invisible particles. Our bound is much stronger than the unitarity bound at the most interesting masses, shows that dark matter halos cannot be significantly modified by annihilations, and can be improved by a factor of 10-100 with existing neutrino experiments.