Systematic Studies using 2‐(1‐Adamantylethynyl)pyrimidine‐5‐carbaldehyde as a Starting Material in Soai’s Asymmetric Autocatalysis

Herein, we present a new substrate for the Soai reaction, which has an adamantylethynyl residue ( 1 g ) and exhibits asymmetric autocatalysis, yielding products with enantiomeric excesses above 99 %. For the first time, all reactions were performed on a parallel synthesizer system to ensure identical reaction conditions. A detailed systematic study of reaction parameters was performed and we report the highest enhancements of enantiomeric excess reported so far in the Soai reaction in one reaction cycle (7.2→94.1 % ee or 3.1→92.1 % ee). Our results led to a set of reaction parameters that yield reproducible results. Therefore, our new starting material 1 g is suitable for systematic and mechanistic studies on this remarkable reaction. A series of experiments designed to quantify the amplification of enantiomeric excess demonstrated that the reaction can be used in principle as a tool for the detection of low enantiomeric excesses: under definite conditions, an unknown low enantiomeric excess (0.1–7 %) was amplified to a detectable one. A back calculation to the original value offers a new method for the determination of small enantiomeric excesses.     

Local magnetic order vs superconductivity in a layered cuprate

We report on the phase diagram for charge-stripe order in La1.6-xNd0. 4SrxCuO4, determined by neutron and x-ray scattering studies and resistivity measurements. From an analysis of the in-plane resistivity motivated by recent nuclear-quadrupole-resonance studies, we conclude that the transition temperature for local charge ordering decreases monotonically with x, and hence that local antiferromagnetic order is uniquely correlated with the anomalous depression of superconductivity at x approximately 1 / 8. This result is consistent with theories in which superconductivity depends on the existence of charge-stripe correlations.