Enynones in organic synthesis. I. Spiroannulation by tandem oxy-cope rearrangement-electrocyclic ring closure

Bis-acetylenic alcohols of proper design undergo a facile oxy-Cope rearrangement to afford mixtures of E- and Z-enynones. These latter compounds afford methylenecyclopentenones upon enolization and electrocyclic ring closure.     

N-Acetylneuraminic Acid: Neoglycoproteins and Pseudopolysaccharides

Abstract

A simplified procedure for the synthesis of acetochloroneuraminic acid is described starting from the methyl ester. N-acetyl neuraminic acid α-allyl glycoside was prepared in high yield using silver salicylate as catalyst. Reductive ozonolysis of the allyl group, followed by direct reductive ami nation to protein carriers, gave immunogenic neoglycoproteins. Copolymerization of the α-allyl glycoside with acrylamide produced a water-soluble pseudopolysaccharide useful for the EL ISA technique.     

Efficient and library-friendly synthesis of furo- and thieno[2,3-d] pyrimidin-4-amine derivatives by microwave irradiation

A new, divergent, efficient, and selective synthesis of furo- and thieno[2,3-d]pyrimidin-4-amine derivatives by microwave irradiation has been developed starting from readily available amines and substituted 2-aminofuran-3-carbonitrile or 2-aminothiophene-3-carbonitrile, which are converted into corresponding formamidines in DMF using benzenesulfonyl chloride.     

The periodic table and the intrinsic barrier in s(n)2 reactions

The identity S(N)2 reactions on nitrogen (see eq 3) with nucleophiles having the general structure H(n)()X(-) where X belongs to the group of nonmetallic elements which do not border the line separating them from the metallic elements (X = F, Cl, Br, I, O, S, Se, N, P, and C) were studied at the G2+ level. The results show that, similarly to the previously observed phenomenon for S(N)2 reaction on carbon (J. Am. Chem. Soc. 1999, 121, 7724), the Periodic Table, through the valence of the element X, controls the intrinsic barrier for the reaction. The average intrinsic barriers obtained for nitrogen substrates were 20, 27, 39, and 57 kcal/mol for the mono-, di-, tri-, and tetravalent X's, respectively. It is also concluded that the intrinsic barriers are similar for N- and C-based substrates and dimethyl substitution on both raises the intrinsic barrier by ca. 10 kcal/mol.     

On the Relation Between Orthogonal,Symplectic and Unitary Matrix Ensembles

For the unitary ensembles of N×N Hermitian matrices associated with a weight function w there is a kernel, expressible in terms of the polynomials orthogonal with respect to the weight function, which plays an important role. For the orthogonal and symplectic ensembles of Hermitian matrices there are 2×2 matrix kernels, usually constructed using skew-orthogonal polynomials, which play an analogous role. These matrix kernels are determined by their upper left-hand entries. We derive formulas expressing these entries in terms of the scalar kernel for the corresponding unitary ensembles. We also show that whenever w/w is a rational function the entries are equal to the scalar kernel plus some extra terms whose number equals the order of w/w. General formulas are obtained for these extra terms. We do not use skew-orthogonal polynomials in the derivations     

The Bergman kernel function: Explicit formulas and zeroes

We show how to compute the Bergman kernel functions of some special domains in a simple way. As an application of the explicit formulas, we show that the Bergman kernel functions of some convex domains, for instance the domain in defined by the inequality , have zeroes.

     

Efficient algorithms for a family of matroid intersection problems

Consider a matroid where each element has a real-valued cost and a color, red or green; a base is sought that contains q red elements and has smallest possible cost. An algorithm for the problem on general matroids is presented, along with a number of variations. Its efficiency is demonstrated by implementations on specific matroids. In all cases but one, the running time matches the best-known algorithm for the problem without the red element constraint: On graphic matroids, a smallest spanning tree with q red edges can be found in time O(n log n) more than what is needed to find a minimum spanning tree. A special case is finding a smallest spanning tree with a degree constraint; here the time is only O(m + n) more than that needed to find one minimum spanning tree. On transversal and matching matroids, the time is the same as the best-known algorithms for a minimum cost base. This also holds for transversal matroids for convex graphs, which model a scheduling problem on unit-length jobs with release times and deadlines. On partition matroids, a linear-time algorithm is presented. Finally an algorithm related to our general approach finds a smallest spanning tree on a directed graph, where the given root has a degree constraint. Again the time matches the best-known algorithm for the problem without the red element (i.e., degree) constraint.     

Tiebout and sympathy

In its simplest form the Tiebout hypothesis suggests that redistribution by local government is not sustainable because individuals, when confronted by negative net fiscal benefits, will vote with their feet, changing their residential locations to jurisdictions which offer a more favorable fiscal balance. It is usually thought, moreover, that they will move (e.g. from central city to suburbs) in descending order of income.Recognition of extended preference modifies this simple characterization of the tiebout process, in which the process of relocation is like ‘peeling an onion’. Any relocation sequence is possible, with either sympathy or antipathy. Even for sympathetic individuals with identical tastes, restrictive and unrealistic assumptions are required to predict, with certainty, that individuals with higher incomes would be the first to move. In particular the marginal tax rate must exceed unity. With antipathy, individuals with lower incomes may move before those with higher incomes, even if net fiscal benefits decrease with income, if they become more willing to begrudge transfers to others as their incomes increase.