Practical syntheses of [1,3,5]‐triazine dendritic molecules on solid supports

A practical and divergent synthesis of supported [1,3,5]‐triazine dendritic molecules on Wang resin, PEGA resin, SynPhase? Lanterns, and silica gel is described. The alkylamine linkers used allow derivatization with functionality for both synthetic (e.g., supported reagent and scavenger activity) and chemical biology applications. The use of supported intermediates allows differentiation of symmetric linkers without the need for protecting group chemistry. The synthetic route uses inexpensive, readily available starting materials in a straightforward and scaleable strategy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2248–2259, 2006     

Sample-path optimization of convex stochastic performance functions

In this paper we propose a method for optimizing convex performance functions in stochastic systems. These functions can include expected performance in static systems and steady-state performance in discrete-event dynamic systems; they may be nonsmooth. The method is closely related to retrospective simulation optimization; it appears to overcome some limitations of stochastic approximation, which is often applied to such problems. We explain the method and give computational results for two classes of problems: tandem production lines with up to 50 machines, and stochastic PERT (Program Evaluation and Review Technique) problems with up to 70 nodes and 110 arcs. Sponsored by the National Science Foundation under grant number CCR-9109345, by the Air Force Systems Command, USAF, under grant numbers F49620-93-1-0068 and F49620-95-1-0222, by the U.S. Army Research Office under grant number DAAL03-92-G-0408, and by the U.S. Army Space and Strategic Defense Command under contract number DASG60-91-C-0144. The U.S. Government has certain rights in this material, and is authorized to reproduce and distribute reprints for Governmental purposes notwithstanding any copyright notation thereon. Sponsored by a Wisconsin/Hilldale Research Award, by the U.S. Army Space and Strategic Defense Command under contract number DASG60-91-C-0144, and the Air Force Systems Command, USAF, under grant number F49620-93-1-0068. Sponsored by the National Science Foundation under grant number DDM-9201813.     

Windmill polynomials over fields of characteristic two

Chambers andSmeets [3] have designed a windmill arrangement of linear feedback shift registers (LFSRs) to generate pn-sequences overGF(2) with high speed. When the windmill hasv vanes, the associated minimal feedback polynomial (having degreen, relatively prime tov) can be taken to have the shapef ₁(x ^v )+x ⁿ f ₂(x ^–v ), where the polynomialsf ₁ andf ₂ have degree [n/v]. Their numerical evidence, whenv is divisible by 4, suggests that, surprisingly, there areno such windmill polynomials which are irreducible ifn±3 (mod 8), while about twice as many irreducible and primitive windmill polynomials as they expected occur ifn±1 (mod 8). A discussion of this behaviour is presented here with proofs. The brief explanation is that the Galois group of the underlying generic windmill polynomial overGF (4) is equal to the alternating groupA _n .     

Geometric techniques in representation theory

A discussion of results and conjectures, focussed around the extension of the modular representation theory for finite Lie-type groups to more general groups that act on building-like geometries.Based on a lecture given at the conference Groups and Geometries-Finite and Algebraic, on 26 March 1986 at Noordwijkerhout, Netherlands (a NATO Advanced Research Workshop).Partially supported by NSF Grant MCS 83-00855.     

A convenient synthesis of a selective gelatinase inhibitor as an antimetastatic agent

Compound 1, 2-(4-phenoxyphenylsulfonylmethyl)thiirane, is a potent and selective inhibitor for human gelatinases (J. Am. Chem. Soc. 2000, 122, 6799-6800), enzymes implicated in a number of diseases, including cancer. This compound is showing excellent promise in animal trials in a number of disease models. Large quantities of this compound were necessary for these studies. A convenient four-step synthetic route for compound 1 is described herein. The synthesis is amenable to scale-up to tens of grams and gives an overall yield of 57% for this important compound.     

Preparation of highly branched poly(vinyl acetate) by transfer to allylic carbonate comonomers

Copolymerization of vinyl acetate with allyl carbonates that contain isopropyl groups yields highly branched poly(vinyl acetates).     

Strong, low-energy two-photon absorption in extended amine-terminated cyano-substituted phenylenevinylene oligomers

Three quadrupolar oligophenylenevinylenes with five rings in the conjugated backbone, terminal donor groups, and various acceptors and/or donors along the backbone were synthesized and their two-photon spectroscopic properties investigated. These chromophores exhibit large two-photon absorption cross sections over a wide wavelength range and two distinct peaks, the strongest of which (deltamax > 3600 GM) is observed at 960-970 nm, a wavelength close to twice the value of the linear absorption maximum (2lambda(1)max). The findings on these chromophores are compared with those for analogous molecules with shorter conjugation length, for which the main two-photon band is at significantly shorter wavelength than 2lambda(1)max.     

N-α-Benzyloxyacetyl derivatives of (S)-4-benzyl-5,5-dimethyloxazolidin-2-one for the asymmetric synthesis of differentially protected α,β-dihydroxyaldehydes

α-Dibenzylamino- and α-benzyloxy- derivatives of N-acetyl-(S)-4-benzyl-5,5-dimethyloxazolidin-2-one readily undergo highly stereoselective boron mediated syn-aldol reactions with a range of aromatic and aliphatic aldehydes, generating the syn-aldol products in good to excellent yields as single diastereoisomers after purification. In the α-dibenzylamino series, deprotection of the functionalised aldol fragments to the corresponding α-amino-β-hydroxy methyl ester or α-amino-β-hydroxyaldehyde proved problematic, with a range of N- and O-protecting groups giving mixtures of products arising from endocyclic and exocyclic cleavage pathways. However, in the α-benzyloxy series, O-silyl protection of the aldol products, and subsequent DIBAL reduction gives stereoselectively the corresponding N-1′-hydroxyalkyloxazolidin-2-ones, which undergo base promoted fragmentation to the desired highly functionalised and differentially protected α,β-dihydroxyaldehydes in good yields and without loss of stereochemical integrity.