Medium ring synthesis by radical ipso-substitution

A new approach to eight and nine membered ring synthesis is described in which a radical ipso-substitution reaction features as a key step.     

Orthogonal self-assembly of low molecular weight hydrogelators and surfactants

The concurrent self-assembly of new 1,3,5-trisamide-cyclohexane-based low molecular weight hydrogelators and various surfactants in water leads to the formation of self-assembled fibrillar networks with encapsulated micelles. This prototype system presents an example of orthogonal self-assembly, that is, the independent formation of two different supramolecular structures, each with their own characteristics that coexist within a single system.     

Are J(Si-H) NMR coupling constants really a probe for the existence of nonclassical H-Si interactions?

A series of hydridosilyl complexes of tantalum, Cp(ArN)Ta(PMe3)(H)(SiClnR3-n) (n = 0-3), was prepared and studied by 29Si NMR, X-ray diffraction, and DFT calculations. An unprecedented increase of the J(Si-H) coupling constant between the hydride and silyl ligands from 14 Hz for n = 0 to 50 Hz n = 3 was observed, which however, according to DFT calculations, does not correspond to stronger bonding interaction between silicon and hydride ligands, with the strongest interaction being for n = 1.     

Transformations of cyclic nonaketides by Aspergillus terreus mutants blocked for lovastatin biosynthesis at the lovA and lovC genes

Two mutants of Aspergillus terreus with either the lovC or lovA genes disrupted were examined for their ability to transform nonaketides into lovastatin 1, a cholesterol-lowering drug. The lovC disruptant was able to efficiently convert dihydromonacolin L 5 or monacolin J 9 into 1, and could also transform desmethylmonacolin J 15 into compactin 3. In contrast, the lovA mutant has an unexpectedly active beta-oxidation system and gives only small amounts of 1 upon addition of the immediate precursor 9, with most of the added nonaketide being degraded to heptaketide 22. Similarly, the lovA mutant does not accumulate the polyketide synthase product 5 and rapidly degrades any 5 added as a precursor via two cycles of beta-oxidation and hydroxylation at C-6 to give 20. The possible involvement of epoxides 21a and 21b in the biosynthesis of 1 was also examined, but their instability in fermentation media and fungal cells will require purified enzymes to establish their role.     

Design and synthesis of a diverse morpholine template library

Efficient and general procedures have been developed for the solution-phase preparation of substituted morpholine derivatives, and a library has been produced around generic structure 1. This library was designed with proprietary modeling software for use as a general screening library. The 30 R1 reagents were phenols, and the 275 R2 reagents were taken from five different reagent classes, giving a variety of product classes in the final library of 8250 potential products. All of the library members were generated from a common intermediate, mesylate (5), which was synthesized efficiently, in bulk, in three steps from N-benzylethanolamine (2). High-throughput chemistry using robotics was carried out to produce the 7907 library members, which were individually characterized by reversed-phase LC/MS analysis.     

Energy transfer at optical frequencies to silicon-on-insulator structures

The refractive-index distribution that is intrinsic to the silicon-on-insulator (SOI) material system makes it possible for optical-frequency guided waves to be confined by the SOI silicon layer. The same refractive-index distribution is unusual among nonmetals in that it is possible for those SOI guided waves to interact strongly with nearby optical-frequency radiators, absorbers, and scatterers (e.g., atoms, molecules, and nanoparticles). We calculate the guided-mode excitation efficiency for an exterior particle near the SOI surface and show that it can attain values greater than 80% under appropriate conditions, thus showing that the SOI waveguide system is an attractive platform for the study of optical-frequency surface interactions.     

Finitely Valued f-Modules, An Addendum

In an -group M with an appropriate operator set it is shown that the -value set (M) can be embedded in the value set (M). This embedding is an isomorphism if and only if each convex -subgroup is an -subgroup. If (M) has a.c.c. and M is either representable or finitely valued, then the two value sets are identical. More generally, these results hold for two related operator sets ₁ and ₂ and the corresponding -value sets and . If R is a unital -ring, then each unital -module over R is an f-module and has exactly when R is an f-ring in which 1 is a strong order unit.