Non-directed, carbonate-mediated C-H activation and aerobic C-H oxygenation with Cp*Ir catalysts.

The effect of oxidatively stable L- and X-type additives on the activity of Cp*Ir catalyst precursors in the C-H activation of arenes has been studied. Turnover numbers for C-H activation of up to 65 can thus be achieved, as determined by H/D exchange in MeOH-D4. In particular, carbonate additives are found to enhance the C-H activation reactivity of Cp*Ir(H2O)3(OTf)2 () more significantly than L-type ligands investigated in this study. Based on these studies, Cp*Ir/carbonate systems are developed that catalyze the aerobic Csp(3)-H oxygenation of alkyl arenes, employing air as oxidant.

Non-directed aromatic C-H amination: catalytic and mechanistic studies enabled by Pd catalyst and reagent design.

This manuscript describes the systematic development of pyridine-type ligands, which promote the Pd catalyzed, non-directed amination of benzene in combination with novel, hydroxylamine-based electrophilic amination reagents. DFT calculations and mechanistic experiments provide insights into the factors influencing the arene C-H amination protocol.

Differential forebrain c-fos mRNA induction by ether inhalation and novelty: evidence for distinctive stress pathways.

Previous studies indicate the existence of subtypes of stressors invoking distinct patterns of neuronal integration. Pathways activated by stress appear to depend on whether the perceived threat is processive/neurogenic or systemic in nature. To test this hypothesis, the present study compares magnitude and extent of c-fos mRNA induction in response to novelty (open field (OF), representing a processive stressor) or ether exposure (representing a systemic stressor). Exposure to the OF or ether fumes both produced increases in plasma corticosterone (CORT) levels; notably, peak levels of secretion were elevated in the ether group, suggestive of augmented HPA secretory activity to this stressor. In situ hybridization analysis of c-fos mRNA induction reveals common and divergent activational properties in the two stress groups. The extent of c-fos mRNA expression was similar in the paraventricular nucleus (PVN), despite stress-related differences in CORT secretion. Analysis of the dorsomedial hypothalamic nucleus, suprachiasmatic nucleus (SCN) and limbic sites, specifically, the lateral septum and medial amygdaloid nucleus, indicate greater c-fos mRNA induction in animals exposed to OF stress. The frontoparietal cortex was only forebrain region showing differential activation by ether. Differential c-fos induction was not observed in the medial preoptic area (ventrolateral quadrant), paraventricular thalamus, dorsolateral striatum or hippocampus. The results indicate that processive and systemic stressors differ not only in the patterning of neuronal activation in the CNS, but also in the extent to which selected stress-sensitive regions are induced.