Tandem silylformylation-allyl(crotyl)silylation: a new approach to polyketide synthesis

Tandem intramolecular silylformylation-allyl(crotyl)silylation reactions have been developed that allow the highly efficient synthesis of polyketide fragments. The substrates are subjected to Rh(I)-catalyzed silylformylation to afford β-(diallyl)silyl aldehydes which undergo spontaneous uncatalyzed allylsilylation. This unusual spontaneous allylsilylation reaction is driven by strain release Lewis acidity, which arises from the ∼95° O-Si-C bond angle in the oxasilacyclopentane product of the silylformylation reaction. The methodology has been developed both for alkene and alkyne substrates, may be used to establish as many as three stereocenters, and has been shown to be amenable to use in an iterative fashion.     

Material compatibility constraints for make-to-order production planning

This paper defines a set of material compatibility constraints for use in order promising mixed integer programs. The constraints always represent a necessary condition for compatibility and, in certain cases, are both necessary and sufficient. The underlying analysis represents incompatibilities using bipartite graphs and applies results from the perfectly matchable subgraph polytope.     

Regression quantiles for unstable autoregressive models

This paper investigates regression quantiles (RQ) for unstable autoregressive models. The uniform Bahadur representation of the RQ process is obtained. The joint asymptotic distribution of the RQ process is derived in a unified manner for all types of characteristic roots on or outside the unit circle. It involves stochastic integrals in terms of a sequence of independent and identically distributed multivariate Brownian motions with correlated components. The related L-estimator is also discussed. The asymptotic distributions of the RQ and the L-estimator corresponding to the nonstationary componentwise arguments can be transformed into a function of a normal random variable and a sequence of i.i.d. univariate Brownian motions. This is different from the analysis based on the LSE in the literature. As an auxiliary theorem, a weak convergence of a randomly weighted residual empirical process to the stochastic integral of a Kiefer process is established. The results obtained in this paper provide an asymptotic theory for nonstationary time series processes, which can be used to construct robust unit root tests.     

Electromagnetic Field Theory Without Divergence Problems 2. A Least Invasively Quantized Theory

Classical electrodynamics based on the Maxwell–Born–Infeld field equations coupled with a Hamilton–Jacobi law of point charge motion is partially quantized. The Hamilton–Jacobi phase function is supplemented by a dynamical amplitude field on configuration space. Both together combine into a single complex wave function satisfying a relativistic Klein–Gordon equation that is self-consistently coupled to the evolution equations for the point charges and the electromagnetic fields. Radiation-free stationary states exist. The hydrogen spectrum is discussed in some detail. Upper bounds for Born's “aether constant” are obtained. In the limit of small velocities of and negligible radiation from the point charges, the model reduces to Schrödinger's equation with Coulomb Hamiltonian, coupled with the de Broglie–Bohm guiding equation.     

Sugar conjugates of fulvestrant (ICI 182,780): efficient general procedures for glycosylation of the fulvestrant core

We have prepared glucose and cellobiose conjugates at the phenolic 3- and hydroxylic 17-positions of the pure anti-estrogenic compound fulvestrant (ICI 182,780), which has recently been approved in the USA for the treatment of advanced postmenopausal breast cancer. Glycosylation at the 17-position was achieved most effectively using pivaloyl protection of the sugar imidates employed, which we found suppressed the competing transacylation reaction and led to improved yields of the product glycosides.     

Second Dissociation Constant of Bis-[(2-hydroxyethyl)amino]acetic Acid (BICINE) and pH of Its Buffer Solutions from 5 to 55 °C

The values of the second dissociation constant, K ₂, and related thermodynamic quantities of the ampholyte bis[(2-hydroxyethyl)amino]acetic acid (BICINE) have been determined at temperatures from 5 to 55 ^∘C. The pH values of six equimolal buffer solutions, and four buffer solutions having ionic strengths (I = 0.16 mol⋅kg⁻¹) similar to those in blood plasma, have been evaluated at 12 temperatures from 5 to 55 ^∘C using the Bates–Guggenheim convention. The liquid junction potentials (E _j ) between the buffer solutions of BICINE and saturated KCl solution of the calomel electrode at 25 and 37 ^∘C have been estimated by measurement with a flowing junction cell. These values of E _j have been used to ascertain the operational pH values at 25 and 37 ^∘C. The pK ₂ values at 25 and 37 ^∘C are 8.333 and 8.156, respectively. The thermodynamic quantities associated with the second acid dissociation have been calculated from the values of pK ₂ as a function of temperature. The zwitterionic buffer BICINE was shown to be useful as a pH standard in the region close to that of blood serum.     

Independence and graph homomorphisms graph homomorphisms

A graph with n vertices that contains no triangle and no 5-cycle and minimum degree exceeding n/4 contains an independent set with at least (3n)/7 vertices. This is best possible. The proof proceeds by producing a homomorphism to the 7-cycle and invoking the No Homomorphism Lemma. For k ≥ 4, a graph with n vertices, odd girth 2k+1, and minimum degree exceeding n/(k+1) contains an independent set with at least kn/(2k+1) vertices; however, we suspect this is not best possible. © 1993 John Wiley & Sons, Inc.     

On the free boundary of surfaces with bounded mean curvature: the non-perpendicular case

H?lder continuity up to the free boundary is proved for minimizing solutions if they meet the supporting surface in an angle which is bounded away from zero. The problem is localized by proving the continuity of the distance function, a result which is also true for stationary points. Received: 14 April 1998     

Sample path analysis of level crossings for the workload process

We examine level crossings of sample paths of queueing processes and investigate the conditions under which the limiting empirical distribution for the workload process exists and is absolutely continuous. The connection between the density of the workload distribution and the rate of downcrossings is established as a sample path result that does not depend on any stochastic assumptions. As a corollary, we obtain the sample path version of the Takács formula connecting the time and customer stationary distributions in a queue. Defective limiting empirical distributions are considered and an expression for the mass at infinity is derived.This research has been supported in part by NSF Grants ECS-8811003 and DDM-8905638.