Silyloxymethanesulfinate as a sulfoxylate equivalent for the modular synthesis of sulfones and sulfonyl derivatives.

An efficient protocol for the modular synthesis of sulfones and sulfonyl derivatives has been developed utilizing sodium tert-butyldimethylsilyloxymethanesulfinate (TBSOMS-Na) as a sulfoxylate (SO2 2-) equivalent. TBSOMS-Na, easily prepared from the commercial reagents Rongalite™ and TBSCl, serves as a potent nucleophile in S-alkylation and Cu-catalyzed S-arylation reactions with alkyl and aryl electrophiles. The sulfone products thus obtained can undergo the second bond formation at the sulfur center with various electrophiles without a separate unmasking step to afford sulfones and sulfonyl derivatives such as sulfonamides and sulfonyl fluorides.

Rhodium-Catalyzed Tandem Addition-Cyclization-Rearrangement of Alkynylhydrazones with Organoboronic Acids.

Transition metal-mediated catalysis routinely enables substrates of multiple π-systems to be efficiently coupled with various carbon nucleophiles along with simultaneous ring formation. This transformation, however, remains unexplored in connection with pericyclic processes. Reported here is a protocol for cycloalkene synthesis based on the merger of rhodium catalysis and a retro-ene reaction. The approach allows alkyne-tethered hydrazones and organoboronic acids to undergo a cascade of addition-cyclization-rearrangement reactions to provide cycloalkene products. The process is initiated by the rhodium-catalyzed addition-cyclization and completed with the allylic diazene rearrangement. The reaction can also be rendered asymmetric by using chiral diene ligands for the rhodium catalyst, whereby enantioselective addition to the C═N bond establishes the C-N stereocenter whose chirality is transferred to an allylic C-H center via suprafacial rearrangement.

Tandem Diels-Alder and retro-ene reactions of 1-sulfenyl- and 1-sulfonyl-1,3-dienes as a traceless route to cyclohexenes.

A pericyclic approach for the synthesis of six-membered ring structures is described. The method employs 1,3-dienes with a 1-sulfur substituent in a tandem sequence of Diels-Alder and retro-ene reactions. In this pairing of [4 + 2] cycloaddition and 1,5-sigmatropic rearrangement, 1-sulfenyl-1,3-dienes engage in Diels-Alder reactions with electron-deficient dienophiles. Subsequently, the sulfenyl group of the cycloadducts is oxidized and unmasked to form allylic sulfinic acids, which undergo sterospecific reductive transposition via sulfur dioxide extrusion. The sequence can also include an inverse electron demand Diels-Alder reaction by using a 1-sulfonyl-1,3-diene. This combination of two pericyclic events offers novel stereocontrolled access to cyclohexenes that are inaccessible via a direct [4 + 2] cycloaddition route.

Effect of postnatal treadmill exercise on c-Fos expression in the hippocampus of rat pups born from the alcohol-intoxicated mothers.

Maternal alcohol-intoxication during pregnancy exerts detrimental effects on fetal development and is known to influence learning ability and memory capability by altering neuronal activity in the hippocampus. c-Fos expression represents neuronal activity and plays a crucial role in the brain development. Physical exercise is known to enhance neuronal plasticity and activity. In the present study, we investigated the influence of postnatal treadmill running on the c-Fos expression in the hippocampus of rat pups born from the alcohol-intoxicated mothers. The results obtained show that maternal alcohol-intoxication suppressed c-Fos expression in the hippocampus of rat pups and that postnatal treadmill exercise enhanced c-Fos expression in the hippocampus of these rat pups. The present study suggests that exercise should be considered as a therapeutic means of countering the effects of maternal alcohol-intoxication, and that it may provide a useful strategy for enhancing the neuronal activity of children born from the mothers who abuse alcohol during pregnancy.

Effects of acupuncture on the intrastriatal hemorrhage-induced caspase3 expression and newly cell birth in rats.

BACKGROUND: Intracerebral hemorrhage is one of the most devastating types of stroke. Caspases are essential players in apoptotic cell death both as initiators and executioners. The v-Fos FBJ murine osteosarcoma viral oncogene homolog (Fos, c-Fos) is an immediate early gene, and Fos expression is sometimes used as a marker for stimuli-induced changes in the metabolic activity of neurons. The expressions of caspase3 and Fos are enhanced with neuroregeneration and with neuronal cell death, respectively. Cells proliferation the dentate gyrus of adult rodents is enhanced by certain pathologic events as seizures and ischemic insult, and such up-regulation of cell proliferation occurring during pathologic situations is thought to be a compensatory response to lesion-induced cell death in the brain. In the present study, we investigated the effects of acupuncture on the intrastriatal hemorrhage-induced caspase3 expression in the striatum and on the Fos expression and cell proliferation in the dentate gyrus of rats. METHODS: For this study, immunohistochemistry for caspase3, Fos and 5-bromo-2'-deoxyuridine (BrdU) was performed. RESULTS: Caspase3 expression in the striatum was increased by intrastriatal hemorrhage. Fos expression and cell proliferation in the dentate gyrus of rats with intracerebral hemorrhage were also increased. Acupunctural treatment, especially at the ST36 acupoint, suppressed the intracerebral hemorrhage-induced caspase3 expression in the stratum, and it also inhibited expression of Fos and cell proliferation in the dentate gyrus. CONCLUSION: In the present study, we have shown that acupuncture treatment has a neuroprotective effect on intrastrstriatal hemorrhage-induced neuronal cell death, and this suggests that acupuncture can aid in the recovery of the central nervous system following stroke.