Synthetic studies on thiostrepton family of peptide antibiotics: synthesis of the dihydroquinoline portion of thiostrepton, the siomycins, and the thiopeptins

Synthesis of the dihydroquinoline portion of thiostrepton, the siomycins, and the thiopeptins, members of the thiostrepton family of peptide antibiotics, has been achieved featuring the one-pot olefination via the Matsumura-Boekelheide rearrangement “using trifluoromethanesulfonic anhydride and triethylamine” and the stereoselective addition reaction controlled by the stereocenter of the peri-position.     

Synthetic studies on oligomycins. Enantiospecific synthesis of the oligomycin B spiroketal portion and establishment of the absolute stereochemistry of oligomycin B

The enantiospecific synthesis of the oligomycin B degradation product 2, corresponding to the C19–C34 spiroketal portion, has been achieved by sequential coupling of the C19–C21, C22–C27, and C28–C34 subunits, establishing the absolute stereochemistry of oligomycin B.     

The structure of arugomycin,a new anthracycline antibiotic part I. structural elucidation of degradation products,AG1, AG2 and AG3.

Based on ¹H- and ¹³C-NMR and mass spectral analysis and chemical degradation, the structures of degradation products of arugomycin (arugorol, AG1, AG2 and AG3) have been determined as shown in Fig. 1.     

Phenylselenenyl chloride in acetonitrile-water : A highly convenient reagent for hydroxyselenation of olefins and preparation of cyclic ethers from dienes

The reaction of phenylselenenyl chloride with olefins in aqueous acetonitrile affords β-hydroxyalkyl phenyl selenides in excellent yields, providing the most convenient method for hydroxyselenation of olefins so far reported. When the reaction was applied to conjugated dienes, monohydroxyselenated products were obtained in good to excellent yields. From non-conjugated dienes, on the other hand, cyclic ethers containing two phenylseleno groups were produced in good to excellent yields, the first step of this reaction being the hydroxyselenation of one double bond.     

Selective 1,4-diacetoxylation of conjugated dienes with tellurium (IV) oxide

Oxidation of several linear conjugated dienes with tellurium (IV) oxide and lithium bromide in acetic acid affords an isomeric mixture of the corresponding diacetoxyalkenes (1,2- and 1,4-addition products), 1,4-isomer being highly selectively produced when the ratio of LiBr/TeO₂, is 5–10.     

A mild photoactivated hydrophilic/hydrophobic switch

Surface modification using light is one of the most powerful methods for controlling the physical and chemical properties offunctionalized surfaces. In this paper, we report on systems where soft UV irradiation (lambda = 365 nm) converts a "low" activity fluorocarbon to a "high" activity amine-functionalized surface. An amine-functionalized SAM (self-assembled monolayer) is first masked using a tertiary amine catalyzed reaction with an N-hydroxysuccinimidyl carbonyl reagent. This mild, room-temperature reaction introduces a hydrophobic photocleavable nitrobenzyl "protecting group" terminated with a fluorocarbon end-chain. UV irradiation (lambda = 365 nm) of this hydrophobic/fluorocarbon surface cleaves the nitrobenzyl residue, returning the surface to the original hydrophilic/amine-functionalized state. This provides a mild, generic method of producing surfaces with hydrophilic/hydrophobic patterns or patterned with amine functional residues. Two different protecting groups, one terminated with a single and the other with three fluorocarbon end chains, are compared. In the case of the more bulky protecting group, only a small proportion of the amine residues react, but the surface is equally hydrophobic and the amine residues equally well shielded from further reaction. Surfaces are characterized by X-ray photoelectron spectroscopy, ellipsometry, surface potential, and contact angle measurements. Images of the photopatterned SAMs were obtained using scanning electron microscopy.     

Palladium-catalyzed allylic oxidation of olefins by t-butyl hydroperoxide and tellurium(IV) oxide

Treatment of several cyclic olefins, β-pinene, allylbenzene, and estragole with palladium(II) salt in acetic acid in the presence of t-butyl hydroperoxide and tellurium(IV) oxide afforded mainly the corresponding allylic acetates. The reaction proceeded catalytically with palladium(II) salt, t-BuOOH working as a reoxidizing agent.     

Carbon-13 NMR spectra of some epoxides derived from dicyclopentadiene

The ¹³C NMR spectra of a series of epoxides derived from endo- and exo-dicyclopentadiene and their partially hydrogenated compounds were determined to examine the substituent effects arising from the introduction of the oxirane ring in comparison with those found in other ring systems. The ¹³C signals of some epoxides were assigned by using lanthanide shift reagents. Characteristic substituent effects exerted by an oxirane ring were demonstrated. Marked steric γ-effects of ?8—13 ppm were observed at the bridge carbon signal in the bicyclo[2.2.1]heptane skeleton. Differences were found in the substituent effects between endo- and exo-dicyclopentadiene epoxides, and have been discussed in relation to the molecular geometry.     

Optomechanical wavelength and energy conversion in high- double-layer cavities of photonic crystal slabs

We demonstrate that ultrasmall double-layer photonic-crystal-slab cavities exhibit a very high-Q value for a wide range of the layer spacing, which enables us to realize unique optomechanical coupling. By mechanically varying the separation, we can achieve extraordinarily large wavelength conversion. In addition, the light stored in the cavity can generate a large radiation force. We show that this system exhibits extremely high energy conversion efficiency between optical and mechanical energy, leading to a novel approach for the optomechanical control of light and matter.