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BACKGROUND Atopic dermatitis (AD) is a pruritic chronic condition associated with significant sleep disturbance, inattention, and sometimes behavioral problems. Enhancing resiliency in children with AD may promote coping strategies to improve quality of life. One strategy for strengthening resiliency is via positive psychology. OBJECTIVE Our objective was to identify positive psychology concepts mentioned by children with AD and their parent to inform strategies to strengthen resiliency in children with AD. METHODS Twenty patient-parent dyads were interviewed to provide feedback on a novel brief Cognitive Behavioral Therapy (CBT) intervention for itch rumination. Patients were 8-17 years-old and diagnosed with AD. Trained coders analyzed transcripts using a coding dictionary developed based on Seligman’s PERMA (Positive emotion, Engagement, Relationships, Meaning, Achievement) model of positive psychology. The frequency of unprompted mentions of PERMA themes and relevant quotations were captured. Transcripts were also separately coded for resiliency, the ultimate goal of PERMA. RESULTS Positive psychology concepts were mentioned by 100% of children and 95% of parents. Engagement and relationships, both negative and positive aspects, were the most common unprompted PERMA themes mentioned by children (70%) and parents (65%). Emotion elicited the most negative comments from children (95%) and parents (85%). When analyzed for resiliency, 8 participants were identified with at least one resiliency code. On average, participants with a resiliency code versus none mentioned PERMA concepts 9.1±4.7 times versus 5.9±4.6 (p = 0.14). When participants were stratified by disease severity, positive psychology concepts were mentioned more by mild patients vs moderate patients vs severe patients, 13±3.0 vs 6.2±4.9 vs 6.13±4.0, respectively (p = 0.034). CONCLUSIONS Among PERMA themes, engagement and relationships are the two most commonly mentioned categories for children with AD. Strategies targeting PERMA such as affirmations and positive reframing may improve psychosocial wellbeing and resiliency in pediatric AD. Future directions will look at incorporating “positive medicine” in AD treatment to not only relieve symptoms but also strengthen positive aspects of life.

Transition metal catalysed allylic substitution is one of the most powerful and frequently used methods in organic synthesis. In particular, palladium-catalysed allylic functionalization has become a well-established strategy for constructing carbon–carbon or carbon–heteroatom bonds, and its utility has been demonstrated in natural product synthesis, drug discovery and materials science. Several methods have been developed to generate π-allylpalladium complexes through ionic mechanisms; however, these methods typically require either prefunctionalized starting materials or stoichiometric oxidants, which naturally limits their scope. Here, we show a radical approach for the generation of π-allylpalladium complexes by employing N-hydroxyphthalimide esters as bifunctional reagents in combination with 1,3-dienes. Using this strategy, we report the 1,4-aminoalkylation of dienes. The remarkable scope and functional group tolerance of this redox-neutral and mild protocol was demonstrated across >60 examples. The utility of this strategy was further demonstrated in radical cascade reactions and in the late-stage modification of drugs and natural products. Palladium-catalysed allylic substitution is a widely used method in organic synthesis, although it requires prefunctionalized starting materials or stoichiometric oxidants. Here the authors report a radical route to form π-allylpalladium complexes, and develop a 1,4-aminoalkylation of dienes under redox-neutral conditions.

A user-friendly, nickel-catalyzed reductive amidation of unactivated primary, secondary, and tertiary alkyl bromides with isocyanates is described. This catalytic strategy offers an efficient synthesis of a wide range of aliphatic amides under mild conditions and with an excellent chemoselectivity profile while avoiding the use of stoichiometric and sensitive organometallic reagents.

BACKGROUND Care coordination can be highly challenging to carry out. When care is fragmented across health systems and providers, there is an increased likelihood of hospital readmissions and wasteful health care spending. During and after care transitions, smartphones have the potential to bolster information transfer and care coordination. However, little research has examined patients’ perceptions of using smartphones to coordinate care. OBJECTIVE This study’s primary objective was to explore patient acceptability of a smartphone app that could facilitate care coordination in a safety net setting. Our secondary objective was to identify how clinicians and other members of primary care teams could use this app to coordinate care. METHODS This qualitative study was conducted at a federally qualified health center in metropolitan Chicago, IL. We conducted four focus groups (two in English, two in Spanish) with high-risk adults who owned a smartphone and received services from an organizational care management program. We also conducted structured interviews with clinicians and a group interview with care managers. Focus groups elicited patients’ perceptions of a smartphone app designed to: (1) identify emergency department (ED) visits and inpatient stays using real-time location data; (2) send automated notifications (ie, alerts) to users’ phones, asking whether they were a patient in the hospital; and (3) send automated messages to primary care teams to notify them about patients’ confirmed ED visits and inpatient stays. Focus group transcripts were coded based on emergent themes. Clinicians and care managers were asked about messages they would like to receive from the app. RESULTS Five main themes emerged in patient focus group discussions. First, participants expressed a high degree of willingness to use the proposed app during inpatient stays. Second, participants expressed varying degrees of willingness to use the app during ED visits, particularly for low acuity ED visits. Third, participants stated their willingness to have their location tracked by the proposed app due to its perceived benefits. Fourth, the most frequently mentioned barriers to acceptability were inconveniences such as “false alarm” notifications and smartphone battery drainage. Finally, there was some tension between how to maximize usability without unnecessarily increasing user burden. Both clinicians and care managers expressed interest in receiving messages from the app at the time of hospital arrival and at discharge. Clinicians were particularly interested in conducting outreach during ED visits and inpatient stays, while care managers expressed more interest in coordinating postdischarge care. CONCLUSIONS High-risk primary care patients in a safety net setting reported a willingness to utilize smartphone location tracking technology to facilitate care coordination. Further research is needed on the development and implementation of new smartphone-based approaches to care coordination.

International audience; The recognition properties of heteroditopic hemicryptophane hosts towards anions, cations, and neutral pairs, combining both cation-pi and anion-pi interaction sites, were investigated to probe the complexity of interfering weak intermolecular interactions. It is suggested from NMR experiments, and supported by CASSCF/CASPT2 calculations, that the binding constants of anions can be modulated by a factor of up to 100 by varying the fluorination sites on the electron-poor aromatic rings. Interestingly, this subtle chemical modification can also reverse the sign of cooperativity in ion-pair recognition. Wavefunction calculations highlight how short-and long-range interactions interfere in this recognition process, suggesting that a disruption of anion-p interactions can occur in the presence of a co-bound cation. Such molecules can be viewed as prototypes for examining complex processes controlled by the competition of weak interactions.

(Carbo) nucleoside derivatives constitute an important class of pharmaceuticals, yet there are only few convergent methods to access new analogues. Here, we report the first synthesis of thymine-, uracil-, and 5-fluorouracil-substituted diester donor-acceptor cyclopropanes and their use in the indium-and tin-catalyzed [3+2] annulations with aldehydes, ketones, and enol ethers. The obtained diester products could be easily decarboxylated and reduced to the corresponding alcohols. The method gives access to a broad range of new (carbo) nucleoside analogues in only four or five steps and will be highly useful for the synthesis of libraries of bioactive compounds.

In this Letter, we describe the synthesis of new donor-acceptor substituted cyclopropanes bearing various imido groups and their use in [3+2]-annulation reactions. A sequence of palladium-catalyzed vinylation and rhodium-catalyzed cyclopropanation gave access to the required cyclopropanes in only two steps and high overall yields. The obtained compounds were used successfully in the tin-catalyzed [3+2] annulation with enol ethers to give cyclopentylamine derivatives in 22–95% yield.

A catalytic hydroamidation of alkynes with isocyanates using alkyl bromides as hydride sources has been developed. The method turns parasitic β-hydride elimination into a strategic advantage, rapidly affording acrylamides with excellent chemo- and regioselectivity.

A user-friendly, nickel-catalyzed reductive amidation of unactivated primary, secondary, and tertiary alkyl bromides with isocyanates is described. This catalytic strategy offers an efficient synthesis of a wide range of aliphatic amides under mild conditions and with an excellent chemoselectivity profile while avoiding the use of stoichiometric and sensitive organometallic reagents.

The sustainable utilization of available feedstock materials for preparing valuable compounds holds great promise to revolutionize approaches in organic synthesis. In this regard, the implementation of abundant and inexpensive carbon dioxide (CO2) as a C1 building block has recently attracted considerable attention. Among the different alternatives in CO2 fixation, the preparation of carboxylic acids, relevant motifs in pharmaceuticals and agrochemicals, is particularly appealing, thus providing a rapid and unconventional entry to building blocks that are typically prepared via waste-producing protocols. While significant advances have been realized, the utilization of simple unsaturated hydrocarbons as coupling partners in carboxylation events is undoubtedly of utmost academic and industrial relevance, as two available feedstock materials can be combined in a catalytic fashion. This review article aims to describe the main achievements on the direct carboxylation of unsaturated hydrocarbons with CO2 by using cheap and available Ni or Fe catalytic species.

Background: Care coordination can be highly challenging to carry out. When care is fragmented across health systems and providers, there is an increased likelihood of hospital readmissions and wasteful health care spending. During and after care transitions, smartphones have the potential to bolster information transfer and care coordination. However, little research has examined patients’ perceptions of using smartphones to coordinate care. Objective: This study’s primary objective was to explore patient acceptability of a smartphone app that could facilitate care coordination in a safety net setting. Our secondary objective was to identify how clinicians and other members of primary care teams could use this app to coordinate care. Methods: This qualitative study was conducted at a federally qualified health center in metropolitan Chicago, IL. We conducted four focus groups (two in English, two in Spanish) with high-risk adults who owned a smartphone and received services from an organizational care management program. We also conducted structured interviews with clinicians and a group interview with care managers. Focus groups elicited patients’ perceptions of a smartphone app designed to: (1) identify emergency department (ED) visits and inpatient stays using real-time location data; (2) send automated notifications (ie, alerts) to users’ phones, asking whether they were a patient in the hospital; and (3) send automated messages to primary care teams to notify them about patients’ confirmed ED visits and inpatient stays. Focus group transcripts were coded based on emergent themes. Clinicians and care managers were asked about messages they would like to receive from the app. Results: Five main themes emerged in patient focus group discussions. First, participants expressed a high degree of willingness to use the proposed app during inpatient stays. Second, participants expressed varying degrees of willingness to use the app during ED visits, particularly for low acuity ED visits. Third, participants stated their willingness to have their location tracked by the proposed app due to its perceived benefits. Fourth, the most frequently mentioned barriers to acceptability were inconveniences such as “false alarm” notifications and smartphone battery drainage. Finally, there was some tension between how to maximize usability without unnecessarily increasing user burden. Both clinicians and care managers expressed interest in receiving messages from the app at the time of hospital arrival and at discharge. Clinicians were particularly interested in conducting outreach during ED visits and inpatient stays, while care managers expressed more interest in coordinating postdischarge care. Conclusions: High-risk primary care patients in a safety net setting reported a willingness to utilize smartphone location tracking technology to facilitate care coordination. Further research is needed on the development and implementation of new smartphone-based approaches to care coordination. [JMIR Mhealth Uhealth 2018;6(5):e112]

Improving the synthesis of complex organic molecules is essential for progress in many fields such as medicine, agrochemicals or materials. Since 2007, our laboratory has been focusing on the development of non-classical bond disconnections based on the use of small, energy-loaded organic molecules: hypervalent iodine reagents and strained rings. In this overview article, we report our progress since 2011 in these areas. The use of cyclic hypervalent iodine reagents has been extended to the C2-selective alkynylation of indoles, the domino cyclization alkynylation of allenes, the alkynylation of thiols and the azidation of carbonyl compounds. Amino-substituted aminocyclopropanes and aminocyclobutanes were used in [3+2] and [4+2] annulations to access nitrogen-rich building blocks, including nucleoside analogues. The first example of dynamic kinetic [3+2] annulation of aminocyclopropanes with both enol ethers and aldehydes was also reported.

In this Letter, we describe the synthesis of new donor-acceptor substituted cyclopropanes bearing various imido groups and their use in [3+2]-annulation reactions. A sequence of palladium-catalyzed vinylation and rhodium-catalyzed cyclopropanation gave access to the required cyclopropanes in only two steps and high overall yields. The obtained compounds were used successfully in the tin-catalyzed [3+2] annulation with enol ethers to give cyclopentylamine derivatives in 22–95% yield.

(Carbo) nucleoside derivatives constitute an important class of pharmaceuticals, yet there are only few convergent methods to access new analogues. Here, we report the first synthesis of thymine-, uracil-, and 5-fluorouracil-substituted diester donor-acceptor cyclopropanes and their use in the indium-and tin-catalyzed [3+2] annulations with aldehydes, ketones, and enol ethers. The obtained diester products could be easily decarboxylated and reduced to the corresponding alcohols. The method gives access to a broad range of new (carbo) nucleoside analogues in only four or five steps and will be highly useful for the synthesis of libraries of bioactive compounds.

The title reaction proceeds with both enol ethers and aldehydes using Cu and a commercially available bisoxazoline ligand.

Cyclization and annulation reactions initiated by ring-opening of small rings, especially cyclopropanes and cyclobutanes are now well-established in synthetic chemistry. Nevertheless, the potential of aminocyclopropanes and cyclobutanes, an important subclass for the synthesis of nitrogen-rich building blocks, has remained unexploited for a long time, despite important pioneering results. In the last decade, the situation has changed dramatically and new catalytic methods have emerged both for cyclization and annulation reactions. The purpose of this feature article is to present recent progress in this area, including our own work using donor-acceptor cyclopropanes and cyclobutanes.

We report the first example of a dynamic kinetic asymmetric [3 + 2] annulation reaction of aminocyclopropanes with both enol ethers and aldehydes. Using a Cu catalyst and a commercially available bisoxazoline ligand, cyclopentyl- and tetrahydrofurylamines were obtained in 69-99% yield and up to a 98:2 enantiomeric ratio using the same reaction conditions. The method gives access to important enantio-enriched nitrogen building blocks for the synthesis of bioactive compounds.

The stereodivergent synthesis of natural product frameworks via a single transformation using simple starting materials is a significant challenge. The prevalence of γ-butyrolactones in biologically active natural products has long motivated the development of enantioselective strategies towards their synthesis. Herein, we report an enantio- and diastereodivergent [3 + 2] annulation reaction for the synthesis of α,β-disubstituted γ-butyrolactones through cooperative N-heterocyclic carbene organocatalysis and iridium catalysis. This method overcomes the challenges of merging N-heterocyclic carbene organocatalysis with iridium catalysis by the appropriate choice of ligands. The use of two chiral catalysts allowed control over the relative and absolute configuration of the two formed stereocentres, thereby providing selective access to all four possible stereoisomers of the γ-lactone products. The transformation could be extended to the synthesis of δ-lactams via [4 + 2] annulation. The synthetic utility of this methodology was illustrated in the concise synthesis of the naturally occurring lignan (−)-hinokinin. Methods to allow access to all isomers of a product are both valuable and challenging to achieve. Here the authors report a catalytic system comprised of an N-heterocyclic carbene and an iridium complex, and show that it can be used for the asymmetric, diastereodivergent synthesis of γ-butyrolactones.

Cyclization and annulation reactions initiated by ring-opening of small rings, especially cyclopropanes and cyclobutanes are now well-established in synthetic chemistry. Nevertheless, the potential of aminocyclopropanes and cyclobutanes, an important subclass for the synthesis of nitrogen-rich building blocks, has remained unexploited for a long time, despite important pioneering results. In the last decade, the situation has changed dramatically and new catalytic methods have emerged both for cyclization and annulation reactions. The purpose of this feature article is to present recent progress in this area, including our own work using donor-acceptor cyclopropanes and cyclobutanes.

Improving the synthesis of complex organic molecules is essential for progress in many fields such as medicine, agrochemicals or materials. Since 2007, our laboratory has been focusing on the development of non-classical bond disconnections based on the use of small, energy-loaded organic molecules: hypervalent iodine reagents and strained rings. In this overview article, we report our progress since 2011 in these areas. The use of cyclic hypervalent iodine reagents has been extended to the C2-selective alkynylation of indoles, the domino cyclization alkynylation of allenes, the alkynylation of thiols and the azidation of carbonyl compounds. Amino-substituted aminocyclopropanes and aminocyclobutanes were used in [3+2] and [4+2] annulations to access nitrogen-rich building blocks, including nucleoside analogues. The first example of dynamic kinetic [3+2] annulation of aminocyclopropanes with both enol ethers and aldehydes was also reported.