Modulable and Highly Diastereoselective Carbometalations of Cyclopropenes

The copper‐catalyzed carbomagnesiation reaction of cyclopropenyl esters 1 leads to various substituted cyclopropanes species 3 in good yields with very high diastereoselectivities. The reaction proceeds through a syn‐chelated carbomagnesiation reaction and could be extended to various cyclopropenylmethyl ester derivatives 5 . The potential of this approach was illustrated by the preparation of two consecutive all‐carbon quaternary stereocenters. However, the carbometalation reaction needs to be performed at temperature ranging from ?35 to ?20 °C to avoid subsequent fragmentation reaction into stereodefined β,γ‐nonconjugated unsaturated esters 4 . Alternatively, the carbocupration reaction with organocopper species could also be performed to leads to configurationally stable cyclopropyl copper species 2[Cu] . Additionally, when the Lewis acid character of the copper center is decreased (i.e., RCuCNLi), the reaction proceed with an anti‐selectivity. The diastereodivergent behavior of these organometallic species is of synthetic interest, since both diastereomers syn‐ 3 and anti‐ 3 can be obtained, at will, from the same precursor cyclopropenyl esters 1 .     

Computational Insights of Selective Intramolecular O-atom Transfer Mediated by Bioinspired Copper Complexes

The stereoselective copper-mediated hydroxylation of intramolecular C−H bonds from tridentate ligands is reinvestigated using DFT calculations. The computational study aims at deciphering the mechanism of C−H hydroxylation obtained after reaction of Cu(I) precursors with dioxygen, using ligands bearing either activated ( L¹ ) or non-activated ( L² ) C−H bonds. Configurational analysis allows rationalization of the experimentally observed regio- and stereoselectivity. The computed mechanism involves the formation of a side-on peroxide species ( P ) in equilibrium with the key intermediate bis-(μ-oxo) isomer ( O ) responsible for the C−H activation step. The P/O equilibrium yields the same activation barrier for the two complexes. However, the main difference between the two model complexes is observed during the C−H activation step, where the complex bearing the non-activated C−H bonds yields a higher energy barrier, accounting for the experimental lack of reactivity of this complex under those conditions.     

The opportunity cost of mean–variance choice under estimation risk

Mean–variance portfolio choice is often criticized as sub-optimal in the more general expected utility framework. It is argued that the expected utility framework takes into consideration higher moments ignored by mean variance analysis. A body of research suggests that mean–variance choice, though arguably sub-optimal, provides very close-to-expected utility maximizing portfolios and their expected utilities, basing its evaluation on in-sample analysis where mean–variance choice is sub-optimal by definition. In order to clarify this existing research, this study provides a framework that allows comparing in-sample and out-of-sample performance of the mean variance portfolios against expected utility maximizing portfolios. Our in-sample results confirm the results of earlier studies. On the other hand, our out-of-sample results show that the expected utility model performs worse. The out-of-sample inferiority of the expected utility model is more pronounced for preferences and constraints under which in-sample mean variance approximations are weakest. We argue that, in addition to its elegance and simplicity, the mean–variance model extracts more information from sample data because it uses the covariance matrix of returns. The expected utility model may reach its optimal solution without using information from the covariance matrix.     

Reagentless amperometric formaldehyde-selective biosensors based on the recombinant yeast formaldehyde dehydrogenase

Novel formaldehyde-selective amperometric biosensors were developed based on NAD(+)- and glutathione-dependent formaldehyde dehydrogenase isolated from a gene-engineered strain of the methylotrophic yeast Hansenula polymorpha. Electron transfer between the immobilized enzyme and a platinized graphite electrode was established using a number of different low-molecular free-diffusing redox mediators or positively charged cathodic electrodeposition paints modified with Os-bis-N,N-(2,2'-bipyridil)-chloride ([Os(bpy)(2)Cl]) complexes. Among five tested Os-containing redox polymers of different chemical structure and properties, complexes of osmium-modified poly(4-vinylpyridine) with molecular mass of about 60 kDa containing diaminopropyl groups were selected. The positively charged cathodic paint exhibited the best electron-transfer characteristics. Moreover, the polymer layers simultaneously served as a matrix for keeping the negatively charged low-molecular cofactors, glutathione and NAD(+), in the bioactive layer. Additionally, covering the enzyme/polymer layer with a negatively charged Nafion membrane significantly decreased cofactors leakage and simultaneously enhanced the sensor' stability. The developed sensors revealed a high selectivity to formaldehyde (FA) and a low cross-sensitivity to other substances (such as, e.g. butyraldehyde, propionaldehyde, acetaldehyde, methylglyoxal). The maximum current value was 34.2+/-0.72 microA/mm(2) (3.05 mm diameter electrode) and the apparent Michaelis-Menten constant (K(M)(app)) derived from the FA calibration curves was 120+/-5mM with a linear detection range for FA up to 20mM. The best observed sensitivity for reagentless sensor was 1.8 nA microM(-1) (358 Am(-2)M(-1)). The developed sensors had a good operational and storage stability. The laboratory prototype of the sensor was applied for FA testing in some real samples of pharmaceutical (formidron), disinfectant (descoton forte) and industrial product (formalin). A good correlation was revealed between the concentration values measured using the developed FdDH-based sensor, an enzymatic method and standard chemical methods of FA determination.     

Asymmetric Catalytic Preparation of Polysubstituted Cyclopropanol and Cyclopropylamine Derivatives

The catalytic asymmetric carbometalation of cyclopropenes followed by either an electrophilic oxidation or amination reaction provides a unique approach to the formation of diastereomerically pure and enantiomerically enriched cyclopropanol and cyclopropylamine derivatives, respectively.     

Noninferior Nash Strategies for Multi-Team Systems

This paper is concerned with the optimization of systems that are controlled by several teams of decision makers. The decision makers within each team cooperate for the benefit of their team. On the other hand, the teams compete among themselves in order to achieve an objective that relates to the overall performance of the system. An approach that merges concepts from team theory and game theory for dealing with such systems and a solution called the noninferior Nash strategy are introduced. This multi-team solution provides a new framework for analyzing hierarchically controlled systems so as to address complicated coordination problems among the decision makers. The properties of the noninferior Nash solution in static multi-team systems are investigated and necessary conditions for its existence are derived. Analytical expressions for the noninferior Nash strategies are derived for a class of linear-quadratic static multi-team games. In order to deal with the issue of nonuniqueness of the solution, the concept of a noninferior Nash strategy with a team leader is introduced. Several examples are presented to illustrate the results.     

On the Stackelberg strategy in nonzero-sum games

The properties of the Stackelberg solution in static and dynamic nonzero-sum two-player games are investigated, and necessary and sufficient conditions for its existence are derived. Several game problems, such as games where one of the two players does not know the other's performance criterion or games with different speeds in computing the strategies, are best modeled and solved within this solution concept. In the case of dynamic games, linear-quadratic problems are formulated and solved in a Hilbert space setting. As a special case, nonzero-sum linear-quadratic differential games are treated in detail, and the open-loop Stackelberg solution is obtained in terms of Riccati-like matrix differential equations. The results are applied to a simple nonzero-sum pursuit-evasion problem.This work was supported in part by the US Air Force under Grant No. AFOSR-68-1579D, in part by NSF under Grant No. GK-36276, and in part by the Joint Services Electronics Program under Contract No. DAAB-07-72-C-0259 with the Coordinated Science Laboratory, University of Illinois, Urbana, Illinois.     

Additional aspects of the Stackelberg strategy in nonzero-sum games

The Stackelberg strategy in nonzero-sum games is a reasonable solution concept for games where, either due to lack of information on the part of one player about the performance function of the other, or due to different speeds in computing the strategies, or due to differences in size or strength, one player dominates the entire game by imposing a solution which is favorable to himself. This paper discusses some properties of this solution concept when the players use controls that are functions of the state variables of the game in addition to time. The difficulties in determining such controls are also pointed out. A simple two-stage finite state discrete game is used to illustrate these properties.This work was supported in part by the U.S. Air Force under Grant No. AFOSR-68-1579D, in part by NSF under Grant No. GK-36276, and in part by the Joint Services Electronics Program under Contract No. DAAB-07-72-C-0259 with the Coordinated Science Laboratory, University of Illinois, Urbana, Illinois.     

A conformationally flexible tetrahydroxycalix[4]arene adopting the unusual 1,3-alternate conformation

The use of a chiral solvating agent enabled the determination of the NMR-silent ring-inversion process of the ketocalixarene 3. Spectroscopic and crystal data indicate that 3 adopts the unusual 1,3-alternate conformation.     

Tris(arylmethyl) derivatives of 1,3,5-trimethoxy- and 1,3,5-triethylbenzene

The hexasubstituted benzenes 7 and 9b were synthesized starting from 3 and 8b, respectively. In the crystal, 9b adopts the fully alternated conformation with all arylmethyl groups oriented syn.