Methylene Thiazolidinediones as Alkylation Reagents in Catalytic C-H Functionalization: Rapid Access to Glitazones.

The straightforward and rapid incorporation of a thiazolidinedione scaffold into prefunctionalized (hetero)aromatic compounds is in demand for the development of antidiabetic glitazones and other pharmaceuticals. Herein, we report the unprecedented N- and O-directed C-H alkylation of various (hetero)arenes with methylene thiazolidinediones under rhodium(III) catalysis. The applicability of the developed protocol in challenging contexts is exhibited by the late-stage installation of a methylene thiazolidinedione moiety on the C-H bond of commercially available drug molecules. Combined mechanistic investigations aided the elucidation of a plausible reaction mechanism.

Transition-Metal-Free Alkylation and Acylation of Benzoxazinones with 1,4-Dihydropyridines.

The direct functionalization of N-heterocycles is a vital transformation for the development of pharmaceuticals, functional materials, and other chemical entities. Herein, the transition-metal-free alkylation and acylation of C(sp2)-H bonds in biologically relevant 2-benzoxazinones with 1,4-dihydropyridines as readily accessible radical surrogates is described. Excellent functional group compatibility and a broad substrate scope were attained. Gram-scale reaction and transformations of the synthesized adducts via Suzuki coupling with heteroaryl boronic acids demonstrated the synthetic potential of the developed protocol.

Site-Selective C8-Alkylation of Quinoline N-Oxides with Maleimides under Rh(III) Catalysis.

The site-selective modification of quinolines and their analogs has emerged as a pivotal topic in medicinal chemistry and drug discovery. Herein, we describe the rhodium(III)-catalyzed C8-alkylation of quinoline N-oxides with maleimides as alkylating agents, resulting in the formation of bioactive succinimide-containing quinoline derivatives. The reaction proceeds under mild conditions with complete functional group tolerance.

Outcomes of Transfemoral Transcatheter Aortic Valve Replacement Performed With General Anesthesia Using a Supraglottic Airway Versus Monitored Anesthesia Care.

OBJECTIVE: Compare general anesthesia with a supraglottic airway versus monitored anesthesia care for transfemoral transcatheter aortic valve replacement (TF-TAVR) in patients with aortic stenosis. The authors hypothesized that the supraglottic airway group would have similar operating room and procedure times, postanesthesia care unit (PACU) and hospital stays, and similar rates of intraprocedural and postprocedural complications compared with the monitored anesthesia care group. STUDY DESIGN: Retrospective chart review with 1:1 propensity score matching of supraglottic airway to monitored anesthesia care patients. SETTING: Tertiary care academic medical center. PARTICIPANTS: TF-TAVR patients between 2017 and 2019. INTERVENTIONS: Supraglottic airway or monitored anesthesia care. MEASUREMENTS AND MAIN RESULTS: One hundred forty-eight supraglottic airway patients were matched with 148 monitored anesthesia care patients. Monitored anesthesia care patients had slightly shorter operating room (p < 0.001) and procedure times (p = 0.015). No difference was observed in hospital length of stay (p = 0.34). Fewer patients in the supraglottic airway group required a PACU stay >2 hours (p < 0.001). Use of intraprocedural vasopressors (p < 0.001) and fentanyl dosage (p < 0.001) was higher in the supraglottic airway group. No differences were observed in postoperative complications or procedural success rates. CONCLUSIONS: In this, the first study to compare these 2 modalities, supraglottic airway use was demonstrated to be a safe, feasible alternative to monitored anesthesia care during TF-TAVR and did not increase organ-specific morbidity, 30-day mortality, hospital length of stay, or PACU length of stay. Even though supraglottic airway was associated with slight increases in procedure and operating room times, these were not clinically significant.

Use of a mixed-method approach to evaluate the implementation of retention promotion strategies in the New York State WIC program.

This research assessed the implementation of strategies piloted at 10 Special Supplemental Nutrition Program for Women, Infants and Children (WIC) clinics aimed at increasing retention in the program, by enhancing participants' shopping experiences. Under WIC Retention Promotion Study: Keep, Reconnect, Thrive (WIC RPS), clinics were recruited and assigned to implement one or a combination of strategies: a standardized Shopping Orientation (SO) curriculum, a Guided Shopping Tour (GST), and a Pictorial Foods Card (PFC) from November 2012 through August 2013. This paper presents results from the process evaluation of the retention strategies, using a mixed-methods comparative case study design employing WIC administrative data, interviews, and focus groups. Qualitative data were inductively coded, analyzed and mapped to the following implementation constructs: organizational capacity, fidelity, allowable adaptations, implementation challenges, and participant responsiveness, while quantitative data were analyzed using SAS to assess reach and dose. Several sites implemented the SO and PFC interventions with the necessary fidelity and dose needed to assess impact on participants' shopping experiences. Sites that were assigned the GST strategy struggled to implement this strategy. However, use of the standardized SO enabled staff to use a "consistent list of shopping tips" to educate participants about the proper use of checks, while use of the PFC increased participants' awareness of the variety of WIC-allowable foods. During follow-up telephone calls, 91 percent of participants reported the shopping tips as helpful. Future analyses will assess the impact of enhanced shopping experience on retention at intervention sites.

Toxic metals in seminal plasma and in vitro fertilization (IVF) outcomes.

We measured toxic metals in seminal plasma collected from 30 men using vitro fertilization (IVF), to evaluate associations with semen quality and IVF outcomes. A doubling in Hg-adjusted Pb concentration was associated with 47% lower total motile sperm. Positive associations were suggested for Hg with pregnancy and live birth, adjusted for Cd or Pb. A negative association was suggested for Hg-adjusted Cd with pregnancy. These data add to evidence indicating that toxic metals impact IVF.