Synthesis of (--)-Muricatacin via alpha- and alpha'-C-H bond functionalization of tetrahydrofuran

(--)-Muricatacin, a potent cytotoxic (4R,5R)-5-hydroxyheptadecan-4-olide, has been synthesized through alpha-C--H hydroxyalkylation and alpha'-C--H oxidation of tetrahydrofuran. This study presents a novel method for C--H bond functionalization as a means for preparing gamma-(hydroxyalkyl)-gamma-butyrolactones.     

Dynamic dendrimer at electrified interface: potential dependent adsorption-desorption and reorientation of a 4-pyridyl-modified PAMAM dendrimer

Potential-dependent dynamic adsorption-desorption and reorientation of a 4-pyridyl modified PAMAM G2 dendrimer at a Au(111) electrode has been demonstrated.     

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.     

Aryne reaction with trifluoromethyl ketones in three modes: C-C bond cleavage, [2+2] cycloaddition and O-arylation

Trifluoromethyl ketones were found to be coupled with arynes in three modes depending upon their substitution patterns, namely C-C bond cleavage, [2+2] cycloaddition and O-arylation.     

Structural confirmation of oligosaccharides newly isolated from sugar beet molasses

ABSTRACT: BACKGROUND: Sugar beet molasses is a viscous by-product of the processing of sugar beets into sugar. The molasses is known to contain sucrose and raffinose, a typical trisaccharide, with a well-established structure. Although sugar beet molasses contains various other oligosaccharides as well, the structures of those oligosaccharides have not been examined in detail. The purpose of this study was isolation and structural confirmation of these other oligosaccharides found in sugar beet molasses. RESULTS: Four oligosaccharides were newly isolated from sugar beet molasses using high-performance liquid chromatography (HPLC) and carbon-Celite column chromatography. Structural confirmation of the saccharides was provided by methylation analysis, matrix-assisted laser desorption/ionaization time of flight mass spectrometry (MALDI-TOF-MS), and nuclear magnetic resonance (NMR) measurements. CONCLUSION: The following oligosaccharides were identified in sugar beet molasses: beta-D-galactopyranosyl-(1- > 6)-beta-D-fructofuranosyl-(2 <-> 1)-alpha-D-glucopyranoside (named beta-planteose), alpha-D-galactopyranosyl-(1- > 1)-beta-D-fructofuranosyl-(2 <-> 1)-alpha-D-glucopyranoside (named1-planteose), alpha-D-glucopyranosyl-(1- > 6)-alpha-D-glucopyranosyl-(1 <-> 2)-beta-D-fructofuranoside (theanderose), and beta-D-glucopyranosyl-(1- > 3)-alpha-D-glucopyranosyl-(1 <-> 2)-beta-D-fructofuranoside (laminaribiofructose). 1-planteose and laminaribiofructose were isolated from natural sources for the first time.     

Real-time measurement of nitric oxide using a bio-imaging and an electrochemical technique

Nitric oxide (NO) is an important mediator responsible for numerous physiological phenomena. Transient levels of NO in biological systems usually range from nanomolar to micromolar concentrations, with a rapid return to basal levels normally seen following these increases. Because NO can diffuse only over a local area in limited time due to such low levels of production and due to its short life-time prior to degradation, high spatial and temporal resolutions are required for direct and continuous NO measurement if the physiological role of NO is to be investigated in any system. For such purposes, analytical methods based on bio-imaging and electrochemical techniques for the measurement of NO are useful. In this paper, we describe the successful application of these methods to a number of biological systems. Specifically, complementary application of these methods demonstrate that it is possible to detect real-time NO production from nervous tissue with high spatial and temporal resolutions.     

Base-free oxidative homocoupling of arylboronic esters

Base-free oxidative homocoupling reaction of arylboronic esters has been found to proceed using a catalytic amount of a palladium-1,3-bis(diphenylphosphino)propane (DPPP) complex under an oxygen atmosphere, affording a variety of biaryls in modest to excellent yields. Even arylboronic esters bearing a base-sensitive functional group are applicable to the reaction.     

Asymmetric sequential Michael reaction: Synthesis of optically active bicyclo[2.2.2]octane derivatives

The sequential Michael reaction of (S)-4,5-di-O-isopropylidenepent-2- enoate and with lithium enolate afforded diastereo- and enantioselectively bicyclo[2.2.2]octane and (or ), respectively. The adducts were efficiently converted into both enantiomeric keto aldehydes (−)- and (+)- .     

Cisplatin suppository: preparation, release characteristics and clinical evaluation

Cisplatin (CDDP) has attracted attention as a chemotherapeutic agent for the treatment of uterine endometrial carcinoma but causes serious side effects, including renal toxicity. CDDP suppositories containing NaCl at different concentrations were prepared to enhance the efficacy and to reduce the side effects of CDDP. The release characteristics, melting point and viscosity of the suppositories were first studied. The rate of CDDP release increased as the NaCl concentration increased: it was 12% 12 h after administration of suppositories containing no NaCl, but 32% with 0.2% NaCl. The melting point was raised by addition of NaCl: 35.5 degrees C without NaCl and 36.5 degrees C with 0.2% NaCl. Addition of 0.2% NaCl doubled the viscosity. Clinically, the suppository containing 0.06% NaCl was given to 3 patients with endometrial carcinoma twice a week for 3 weeks to examine serum CDDP levels and endometrial absorption. Patients with endometrial carcinoma showed different peak plasma platinum (Pt) levels which were as low as 0.12, 0.06 and 0.22 micrograms Pt/ml with similar patterns of change in the level. Radiographic analysis revealed many Pt particles in sections of necrosed endometria after 21d of the treatment. No side effects of CDDP were found in biochemical testing or subjective symptoms.     

Reaction of enaminones with carbon disulfide: Synthesis of heterocycles using enamino dithiocarboxylates

Reaction of various types of enaminones, which are prepared by the condensation of 1,3-dicarbonyl compounds with aromatic amines, with carbon disulfide in the presence of sodium hydroxide as the base in dimethyl sulfoxide to give the corresponding enamino dithiocarboxylates, 1,3-thiazines and trithiones. Enamino dithiocarboxylates are cyclized under refluxing in diphenyl ether to give the fused quinoline derivatives. The reaction of 6-arylamino-1,3-dimethyluracils with excess carbon disulfide in the presence of sodium hydroxide and subsequent methylation with dimethyl sulfate gave directly the corresponding 1,3-dimethyl-5-methylthiopyrimido[4,5-b]quinoline-2,4(1H,3H)-diones.