Intramolecular Pd-Catalyzed Reductive Amination of Enolizable sp3-C-H Bonds.

A palladium-catalyzed reductive cyclization of nitroarenes has been designed to construct sp3-C-NHAr bonds from sp3-C-H bonds by using an enolizable nucleophile to intercept a nitrosoarene intermediate. Exposure of ortho-substituted nitroarenes to 5 mol % of Pd(OAc)2 and 10 mol % of phenanthroline under 2 atm of CO constructs partially saturated 5-, 6-, or 7-membered N-heterocycles using α-pyridyl carboxylates, malonates, 1,3-dimethylbarbituric acid, 1,3-diones, or difurans as the nucleophile.

Nucleophilic Iron Complexes in Proton-Transfer Catalysis: An Iron-Catalyzed Dimroth Cyclocondensation.

The nucleophilic iron complex Bu4 N[Fe(CO)3 (NO)] (TBA[Fe]) is an active catalyst in C-H-amination but also in proton-transfer catalysis. Herein, we describe the successful use of this complex as a proton-transfer catalyst in the cyclocondensation reaction between azides and ketones to the corresponding 1,2,3-triazoles. Cross-experiments indicate that the proton-transfer catalysis is significantly faster than the nitrene-transfer catalysis, which would lead to the C-H amination product. An example of a successful sequential Dimroth triazole-indoline synthesis to the corresponding triazole-substituted indolines is presented.

Iron-Catalyzed Intramolecular Aminations of C(sp3 )-H Bonds in Alkylaryl Azides.

The nucleophilic iron complex Bu4 N[Fe(CO)3 (NO)] (TBA[Fe]) catalyzes the direct intramolecular amination of unactivated C(sp3 )-H bonds in alkylaryl azides, which results in the formation of substituted indoline and tetrahydroquinoline derivatives.

Optimizing exposure-based CBT for anxiety disorders via enhanced extinction: Design and methods of a multicentre randomized clinical trial.

Exposure-based psychological interventions currently represent the empirically best established first line form of cognitive-behavioural therapy for all types of anxiety disorders. Although shown to be highly effective in both randomized clinical and other studies, there are important deficits: (1) the core mechanisms of action are still under debate, (2) it is not known whether such treatments work equally well in all forms of anxiety disorders, including comorbid diagnoses like depression, (3) it is not known whether an intensified treatment with more frequent sessions in a shorter period of time provides better outcome than distributed sessions over longer time intervals. This paper reports the methods and design of a large-scale multicentre randomized clinical trial (RCT) involving up to 700 patients designed to answer these questions. Based on substantial advances in basic research we regard extinction as the putative core candidate model to explain the mechanism of action of exposure-based treatments. The RCT is flanked by four add-on projects that apply experimental neurophysiological and psychophysiological, (epi)genetic and ecological momentary assessment methods to examine extinction and its potential moderators. Beyond the focus on extinction we also involve stakeholders and routine psychotherapists in preparation for more effective dissemination into clinical practice.

Iron-Catalyzed Intramolecular C(sp(2))-H Amination.

The nucleophilic iron complex Bu4N[Fe(CO)3(NO)] (TBA[Fe]) catalyzes the direct intramolecular C-H amination of α-azidobiaryls and (azidoaryl)alkenes into the corresponding carbazoles and indoles, respectively, under mild conditions and with low catalyst loadings. These features and the broad functional-group tolerance render this method a particularly attractive alternative to established noble-metal-based procedures.