Asymmetric Michael Addition of Aldimino Esters with Chalcones Catalyzed by Silver/Xing‐Phos: Mechanism‐Oriented Divergent Synthesis of Chiral Pyrrolines

The mechanism‐oriented reaction design for the divergent synthesis of chiral molecules from simple starting materials is highly desirable. In this work, aromatic amide‐derived nonbiarylatropisomer/silver (silver/Xing‐Phos) complex was used to catalyze the Michael addition of glycine aldimino esters to chalcones and successfully applied to the subsequent cyclocondensation to afford substituted cis‐Δ(1)‐pyrroline derivatives with up to 98 % ee. Besides the inherent performance of the chiral Ag/Xing‐Phos catalyst system, it was found that the workup of such reactions played an important role for the stereoselective construction of stereodivergent Δ(1)‐pyrrolines, in which an epimerization of the cis‐Δ(1)‐pyrrolines to the trans‐isomers during was revealed.     

Likelihood Inference under Generalized Hybrid Censoring Scheme with Comp eting Risks

Statistical inference is developed for the analysis of generalized type-II hybrid censoring data under exponential competing risks model. In order to solve the problem that approximate methods make unsatisfactory performances in the case of small sample size, we establish the exact conditional distributions of estimators for parameters by conditional moment generating function(CMGF). Furthermore, confidence intervals(CIs) are constructed by exact distributions, approximate distributions as well as bootstrap method respectively, and their performances are evaluated by Monte Carlo simulations. And finally, a real data set is analyzed to illustrate all the methods developed here.     

Computational insight into asymmetric uranyl‐salophen coordinated with α, β‐unsaturated aldehydes and ketones

The study of the catalytic activity and activation mechanism of asymmetric uranyl‐salophens with α, β‐unsaturated aldehydes or α, β‐unsaturated ketones, is a research hotspot. In this paper, the complexes of the uranyl–salophen(U‐S) modified by unilateral benzene, coordinated with cyclohexenone, cyclopentenone and acrolein, were investigated using density functional theory calculations at the level of B3LYP/6‐311G(d, p) basis set. The results showed that the uranyl‐salophen(U‐S) weakened the large π bond between C = C and C = O of the α, β‐unsaturated aldehydes and ketones, making the unsaturated aldehydes and ketones activated. In addition, the molecular‐recognition selectivity of the asymmetrical uranyl‐salophen for cyclohexenone and cyclopentenone were much higher than for acrolein.     

Expedient and Diastereodivergent Assembly of Terpenoid Decalin Subunits having Quaternary Stereocenters through Organocatalytic Robinson Annulation of Nazarov Reagent

We report an expedient approach to highly functionalized cis‐ and trans‐decalines that could function as key structural subunits toward the synthesis of various classes of terpenoids. Key to the strategy is an organocatalyzed Robinson annulation reaction of the Nazarov reagent that affords chiral enone building blocks with high enantioselectivities. The quaternary carbon stereogenic center can direct the subsequent reactions and allow the rapid and diastereoconvergent assembly of complex decalines with contiguous stereocenters.     

Making Spiroketal‐based Diphosphine (SKP) Ligands via a Catalytic Asymmetric Approach

The spiro concept for chiral ligand design represents an important contribution to the area of asymmetric catalysis. Due to the considerable difficulties in the construction of enantiopure all‐carbon spiro backbones, the development of catalytic asymmetric synthesis of chiral spiro structures via short steps is highly valuable. Herein we present our studies on the catalytic asymmetric synthesis of aromatic spiroketals and the corresponding diphosphine (SKP) ligands.     

A Finite Volume Implicit Euler Scheme for the Linearized Shallow Water Equations: Stability and Convergence

The linearized shallow water equations are discretized in space by a finite volume method and in time by an implicit Euler scheme. Stability and convergence of the scheme are proved.