Stereoselective Oxidative Bioconjugation of Amino Acids and Oligopeptides to Aldehydes

The first stereoselective, near-equimolar, and metal-free oxidative bioconjugation of amino acids and oligopeptides to aldehydes is presented. Based on a newly developed organocatalytic oxidative concept, the C-terminal and side-chain carboxylic acid functionalities of amino acids and oligopeptides are shown to couple in a stereoselective manner to α-branched aldehydes catalyzed by a chiral primary amine and a quinone as oxidizing agent. The oxidative coupling generally proceeds in high yield. For aspartic acid, selective coupling of the side-chain, or the C-terminal carboxylic acid, is demonstrated depending on the protection strategy. The stereoselective, oxidative bioconjugation concept is extended to a series of oligopeptides where coupling to carboxylic acid functionalities is presented. Bioorthogonal linker molecules for further functionalization are obtained by merging the oxidative coupling strategy with the click concept. It is demonstrated that the configuration of the new stereocenter is determined exclusively by the organocatalyst.     

Weighted Overlap Dominance – A procedure for interactive selection on multidimensional interval data

We present an outranking procedure that supports selection of alternatives represented by multiple attributes with interval valued data. The procedure is interactive in the sense that the decision maker directs the search for preferred alternatives by providing weights of the different attributes as well as parameters related to risk attitude and weighted dominance. The outranking relation builds on pairwise comparisons between optimistic and pessimistic weighted values as well as weighted dominance relations supported by volume based measures. The suggested procedure is referred to as the Weighted Overlap Dominance procedure (WOD).     

Rationing with baselines: the composition extension operator

We introduce a new operator for general rationing problems in which, besides conflicting claims, individual baselines play an important role in the rationing process. The operator builds onto ideas of composition, which are not only frequent in rationing, but also in related problems such as bargaining, choice, and queuing. We characterize the operator and show how it preserves some standard axioms in the literature on rationing. We also relate it to recent contributions in such literature.     

Catalytic Asymmetric Oxidative γ‐Coupling of α,β‐Unsaturated Aldehydes with Air as the Terminal Oxidant

A novel concept for catalytic asymmetric coupling reactions is presented. Merging organocatalysis with single‐electron oxidation by using a catalytic amount of a copper(II) salt and air as the terminal oxidant, we have developed a highly stereoselective carbon–carbon oxidative coupling reaction of α,β‐unsaturated aldehydes. The concept relies on the generation of a dienamine intermediate, which is oxidized to an open‐shell activated species that undergoes highly selective γ‐homo‐ and γ‐heterocoupling reactions. In the majority of examples presented, only a single stereoisomer was formed.     

Truth-telling and Nash equilibria in minimum cost spanning tree models

In this paper we consider the minimum cost spanning tree model. We assume that a central planner aims at implementing a minimum cost spanning tree not knowing the true link costs. The central planner sets up a game where agents announce link costs, a tree is chosen and costs are allocated according to the rules of the game. We characterize ways of allocating costs such that true announcements constitute Nash equilibria both in case of full and incomplete information. In particular, we find that the Shapley rule based on the irreducible cost matrix is consistent with truthful announcements while a series of other well-known rules (such as the Bird-rule, Serial Equal Split, and the Proportional rule) are not.     

Continuous benchmark selections

The existence of benchmark selections that are continuous both in production factors and technology is examined. If the class of technologies display non-convexities, continuous selections do not exist in general. For probabilistic benchmarks, i.e., lotteries over efficient productions, existence of continuous selections holds only under additional conditions of well-behavedness.     

Interacting Wave Fronts and Rarefaction Waves in a Second Order Model of Nonlinear Thermoviscous Fluids

A wave equation including nonlinear terms up to the second order for a thermoviscous Newtonian fluid is proposed. In the lossless case this equation results from an expansion to third order of the Lagrangian for the fundamental non-dissipative fluid dynamical equations. Thus it preserves the Hamiltonian structure, in contrast to the Kuznetsov equation, a model often used in nonlinear acoustics. An exact traveling wave front solution is derived from a generalized traveling wave assumption for the velocity potential. Numerical studies of the evolution of a number of arbitrary initial conditions as well as head-on colliding and confluent wave fronts exhibit several nonlinear interaction phenomena. These include wave fronts of changed velocity and amplitude along with the emergence of rarefaction waves. An analysis using the continuity of the solutions as well as the boundary conditions is proposed. The dynamics of the rarefaction wave is approximated by a collective coordinate approach in the energy balance equation.     

Decarboxylative [4+2] Cycloaddition by Synergistic Palladium and Organocatalysis

A novel reaction based on synergistic catalysis, combining palladium‐ and organocatalysis has been developed. The palladium catalyst activates vinyl benzoxazinanones via a decarboxylation to undergo a [4+2] cycloaddition with iminium‐ion activated α,β‐unsaturated aldehydes. The reaction is demonstrated to proceed for a number of combinations of vinyl benzoxazinanones reacting with α,β‐unsaturated aldehydes, providing highly substituted vinyl tetrahydroquinolines in good to high yields, and excellent enantio‐ and diastereoselectivities (>98 % ee and >20:1 d.r.). The palladium catalyst used in the synergistic catalysis can be re‐used in a one‐pot sequential coupling reaction with an aromatic boronic acid forming the coupling product in 95 % yield, >20:1 d.r. and 99 % ee.     

On the set of Lorenz-maximal imputations in the core of a balanced game

This paper considers the set of Lorenz-maximal imputations in the core of a balanced cooperative game as a solution concept. It is shown that the Lorenz-solution concept satisfies a number of suitable properties such as desirability, continuity and the reduced game property. Moreover, the paper consideres alternative characterizations where it is shown that Lorenz-fairness is tantamount to the existence of an additive, strictly increasing and concave social welfare function. Finally the paper also provides axiomatic characterizations as well as two examples of application. Received: February 1999/Final version: June 2001