Trapping σ-Alkyl-Palladium(II) Intermediates with Arynes Encompassing Intramolecular C-H Activation: Spirobiaryls through Pd-Catalyzed Cascade Reactions.

A palladium-catalyzed cascade reaction based on the trapping of transient alkyl-PdII intermediates with arynes encompassing a C-H activation step has been developed. This synthetic pathway gives rise to hetero-spirocyclic scaffolds containing a biaryl motif, and opens up new synthetic strategies in the design of cascade reactions since it gathers several aspects of Pd chemistry, i.e., intra- and intermolecular carbopalladation of unsaturated species, C-H activation and C-C coupling processes.

Synthesis of Benzofused O- and N-Heterocycles through Cascade Carbopalladation/Cross-Alkylation of Alkynes Involving the C-C Cleavage of Cyclobutanols.

We report a Pd-catalyzed route to heterocycles bearing a tetrasubstituted alkene fragment. Our approach merges the intramolecular carbopalladation of tethered alkynes with an alkylation step produced by the C-C cleavage of cyclobutanol derivatives. An alkenyl-Pd(II) intermediate has been isolated and characterized by X-ray diffraction studies. Interestingly, the nature of the tethering alkynyl chain influences the E/Z stereochemistry of the alkenyl fragment in the functionalized heterocycles.

Effectiveness of kinesio taping in addition to conventional rehabilitation treatment on pain, cervical range of motion and quality of life in patients with neck pain: A randomized controlled trial.

BACKGROUND: Kinesio taping (KT) is a new taping modality frequently used in the clinical setting. However there is contradictory evidence about its effectiveness in patients with neck pain. OBJECTIVE: To determine the effectiveness of KT as a supplementary treatment in addition to conventional rehabilitation in patients with neck pain. METHODS: Forty-five subjects with neck pain were included in this controlled trial and were assigned to the following groups: Kinesio Taping, placebo (P), and conventional rehabilitation control (CR). A daily self-assessment record of perceived pain, medication intake, quality of life and range of motion was registered at baseline, posttreatment and follow-up. RESULTS: Cohen's coefficient showed large effects in terms of reducing pain perception in all three groups. ANOVAs showed that the course of treatment differed across groups only for neck flexion (p= 0.043). We found significant differences in neck flexion when comparing baseline and one-month follow-up values and neck flexion significantly increased in all three groups: KT (p= 0.05); P (p= 0.01); and CR (p= 0.04). Between-group analyses showed no significant differences for any of the measurements. CONCLUSIONS: A protocol of manual therapy and physical exercises, significantly improved pain and mobility in patients with neck pain. We obtained no evidence of additional benefits from the use of KT in this population.

Synthesis of spiro-oxoindoles through Pd-catalyzed remote C-H alkylation using α-diazocarbonyl compounds.

In this communication we describe a new route to spiro-oxoindole derivatives through a novel Pd-catalyzed cascade process. This reaction is based on the remote C-H activation performed by σ-alkyl Pd(ii) species generated in situ via intramolecular carbopalladation of alkenes, followed by insertion of a carbenoid coupling partner.