Thiourea-Catalyzed C-F Bond Activation: Amination of Benzylic Fluorides.

We describe the first thiourea-catalyzed C-F bond activation. The use of a thiourea catalyst and Ti(OiPr)4 as a fluoride scavenger allows the amination of benzylic fluorides to proceed in moderate to excellent yields. Preliminary results with S- and O-based nucleophiles are also presented. DFT calculations reveal the importance of hydrogen bonds between the catalyst and the fluorine atom of the substrate to lower the activation energy during the transition state.

The control of stereochemistry by the pentafluorosulfanyl group.

The influence of pentafluorosulfanylation on biological activity has been revealed in numerous comparative studies of biologically active compounds, but considerably less is known about the influence of pentafluorosulfanylation on reactivity. Among the distinctive properties of the pentafluorosulfanyl group is the profound dipole moment that results from introduction of this substituent. It has been shown that dipolar effects coupled with the steric demand of the SF5 group may be employed to influence the stereochemistry of reactions, especially those processes with significant charge separation in the transition state. The Staudinger ketene-imine cycloaddition reaction is an ideal platform for investigation of dipolar control of diastereoselectivity by the pentafluorosulfanyl group.

Highly regioselective gold-catalyzed formal hydration of propargylic gem-difluorides.

Herein, we report a highly regioselective gold-catalyzed formal hydration of propargylic gem-difluorides. Not only does this transformation provide access to versatile fluorinated building blocks that were difficult or hardly possible to access beforehand, but it also represents a rare case of a highly regioselective gold-catalyzed hydroalkoxylation of internal alkynes and puts forward the utility of the difluoromethylene unit as a directing group in catalysis.

Preparation and characterization of alkenyl aryl tetrafluoro-λ(6) -sulfanes.

Substituted alkenyl aryl tetrafluoro-λ(6) -sulfanes have been prepared by the direct addition of readily accessible chlorotetrafluorosulfanyl arenes to primary alkynes. Substitution of an apical fluorine of the pentafluorosulfanyl group enables modulation of the reactivity of this little explored functional group while at the same time facilitating the direct investigation of aryl substituent effects on the aryl tetrafluorosulfanyl-substituted products.

Use of gauze-based negative pressure wound therapy in a pediatric burn patient.

Negative pressure wound therapy (NPWT) is described as it is used in the treatment of an infant burn victim. This case highlights the ability and techniques used to maintain an airtight dressing seal in the perirectal region. Use of this dressing type post-skin grafting allowed for 100% graft adhesion and no bacterial contamination despite close proximity to the rectum. Favorable experience and outcome with this patient are strong indicators that NPWT should be considered as a viable treatment in pediatric populations and that situations where body contour or fluids may make NPWT difficult to administer should not be a deterrent to therapy.