The Self-catalytic Esterification Reaction of O-Phosphoryl Serine Derivative

O-Phosphoryl serine derivative can perform serf-catalytic esterification reaction in the mixture of CH3OH and CHCl3 at the room temperature. The phosphoryl group participation was the key step of the esterification. This type of reactions were proposed through an intermediate of mixed phosphoric-carboxylic anhydride that might provide a clue to the function of the phosphoryl group in the phosphorylated enzymes and in the prebiotic synthesis of protein.     

Modular and stereoselective formal synthesis of MeBmt, an unusual amino acid constituent of cyclosporin A

A convergent, flexible and stereoselective formal synthesis of MeBmt, the nonproteinogenic amino acid constituent of cyclosporin A is disclosed. The sulfinyl moiety has been exploited as the internal nucleophile to stereo- and regioselectively functionalize an allylic carbamate.     

α-单取代环十二酮肟及缩氨基硫脲的合成及晶体结构

单晶X射线衍射分析表明, α-单取代环十二酮与氨衍生物羟胺和氨基硫脲发生缩合反应得到两种母体构象均为[3333], 而取代基为边外向或角反向的α-单取代环十二酮肟或缩氨基硫脲. 利用底物的“角位羰基参与反应”原理, “记忆效应”及进攻试剂与底物是否形成氢键解释了这一实验结果. 通常情况下, 试剂从空间障碍小的一面进攻羰基而生成α-角反取代环十二酮肟或缩氨基硫脲. 当试剂与底物的取代基之间能够形成分子间氢键时, 则生成α-边外取代环十二酮肟或缩氨基硫脲.     

Forecasting accuracy of behavioural models for participation in the arts

This paper assesses the forecasting performance of count data models applied to arts attendance. We estimate participation models for two artistic activities that differ in their degree of popularity – museums and jazz concerts – with data derived from the 2002 release of the Survey of Public Participation in the Arts for the United States. We estimate a finite mixture model – a zero-inflated negative binomial model – that allows us to distinguish between “true” non-attendants and “goers” and their respective behaviour regarding participation in the arts. We evaluate the predictive (in-sample) and forecasting (out-of-sample) accuracy of the estimated model using bootstrapping techniques to compute the Brier score. Overall, the results indicate the model performs well in terms of forecasting. Finally, we draw certain policy implications from the model’s forecasting capacity, thereby allowing the identification of target populations.     

The Economics of Social Stratification in Premodern Societies

We present a microeconomic model of social stratification, which includes an endogenous fertility component. In the model, egalitarian and stratified societies coexist. The latter are divided into 2 hereditary classes: a warrior elite and a productive class. The model entails that the extra cost warriors must incur to train and equip their children for war determines the relative sizes of both classes and the degree of economic inequality. Higher costs of warrior children imply a greater economic advantage for warriors and a smaller ratio of warriors to producers. These results are consistent with the historical evidence. Finally, we explore conditions under which the social contributions of the warrior elite could discourage a revolution.     

Synthesis and Electrophilic Cyclization Reactions of Diphenyl 3-Methylpenta-1,2,4-trienyl Phosphine Oxide

Diphenyl 3-methyl-penta-1,2,4-trienyl phosphine oxide can be readily prepared via an atom-economical [2,3]-sigmatropic rearrangement of the mediated alkenynyl phosphinite formed in situ by reaction of 3-methylpent-1-en-4-yn-3-ol with diphenylchlorophosphine. Electrophilic cyclization reactions of the vinylallenyl phosphine oxide prepared were investigated as it was established that the reactions proceeded with formation of various heterocyclic or highly unsaturated compounds with participation of the allenic and/or 1,3-dienic part of the vinylallenic system with neighboring group participation of phosphoryl and/or vinylic group.

Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file.     

Entropies and IPR as Markers for a Phase Transition in a Two-Level Model for Atom–Diatomic Molecule Coexistence

A quantum phase transition (QPT) in a simple model that describes the coexistence of atoms and diatomic molecules is studied. The model, which is briefly discussed, presents a second-order ground state phase transition in the thermodynamic (or large particle number) limit, changing from a molecular condensate in one phase to an equilibrium of diatomic molecules–atoms in coexistence in the other one. The usual markers for this phase transition are the ground state energy and the expected value of the number of atoms (alternatively, the number of molecules) in the ground state. In this work, other markers for the QPT, such as the inverse participation ratio (IPR), and particularly, the Rényi entropy, are analyzed and proposed as QPT markers. Both magnitudes present abrupt changes at the critical point of the QPT.     

A new approach to the synthesis of lactams of muramic,isomuramic and normuramic acids via intramolecular O-alkylation: Stereochemical features of the intramolecular nucleophilic substitution

The title compounds were synthesized from the selectively protected N-acylated d-glucosamine derivatives, containing α-halo carboxylic acid moieties, via intramolecular 3-O-alkylation. It was found that if the starting compound contains asymmetric electrophilic center, isomuramic acid derivatives were mainly formed, regardless of the configuration of the electrophilic carbon atom. An explanation for the observed stereochemical results was proposed on the basis of the analysis of steric interactions in the molecules of the starting compounds, as well as using the concept of anchimeric assistance. It was shown that N-acetylation of the obtained lactam derivatives and subsequent methanolysis under mild conditions led to the selective cleavage of δ-lactam ring resulting in the formation of the corresponding ester derivatives of N-acetylmuramic acid or its analogues in high yields.     

The design and synthesis of a novel organophosphorus compound containing the structure of both β-amino acid and β-aminophosphonate

<正>A novel organophosphorus compound containing the structure of bothβ-amino acid andβ-aminophosphonate is designed and synthesized.Arbuzov reaction with P(OEt)_3,the N-Boc protected iodide 3 cannot provide the desired product but 2-oxazolidinone 4 because of the neighboring-group participation of the Boc moiety.To avoid the intramolecular participation of the carbamates,the Ts protecting group is employed and the Ts-protected iodide 5 affords the target product successfully.