The Direct Conversion of Esters to Ketones Enabled by a Traceless Activating Group.

We report here the design and development of a method for the single-step conversion of esters to ketones with simple reagents. The selective transformation of esters to ketones, rather than tertiary alcohols, is made possible by the use of a transient sulfinate group on the nucleophile that activates the adjacent carbon toward deprotonation to form a carbanion that adds to the ester, followed by a second deprotonation to prevent further addition. The resulting dianion undergoes spontaneous fragmentation of the SO2 group upon quenching with water to reveal the ketone product.

How to bargain successfully with adolescents: What can be learned from youth development professionals.

This study examines risks and potential benefits that youth professionals experience in bargaining with adolescents. We conducted semistructured qualitative interviews with 50 experienced adult leaders of 27 high-quality arts, technology, and leadership youth programs (serving ethnically-diverse teens). Half worked with younger teens (ages 11-14), half with older (ages 14-18). Leaders reported bargaining in ways responsive to youth's wants and needs, reaching win-win agreements. Leaders of younger youth experienced more risks in bargaining, so took greater control over what was bargained. They used bargains most often to motivate when youth's enthusiasm dropped, and these bargains sometimes helped youth develop self-motivation. Leaders of older youth reported fewer risks and more benefits. They bargained as equals, asking youth to share decision-making responsibility. They used bargaining as a pedagogical tool to model, support, and challenge youth, which helped build their capacities for deliberative decision-making. The findings illuminate strategies for practitioners to use bargaining effectively.

Carboxyboronate as a Versatile In Situ CO Surrogate in Palladium-Catalyzed Carbonylative Transformations.

The application of carboxy-MIDA-boronate (MIDA=N-methyliminodiacetic acid) as an in situ CO surrogate for various palladium-catalyzed transformations is described. Carboxy-MIDA-boronate was previously shown to be a bench-stable boron-containing building block for the synthesis of borylated heterocycles. The present study demonstrates that, in addition to its utility as a precursor to heterocycle synthesis, carboxy-MIDA-boronate is an excellent in situ CO surrogate that is tolerant of reactive functionalities such as amines, alcohols, and carbon-based nucleophiles. Its wide functional-group compatibility is highlighted in the palladium-catalyzed aminocarbonylation, alkoxycarbonylation, carbonylative Sonogashira coupling, and carbonylative Suzuki-Miyaura coupling of aryl halides. A variety of amides, esters, (hetero)aromatic ynones, and bis(hetero)aryl ketones were synthesized in good-to-excellent yields in a one-pot fashion.

How challenges and peers contribute to social-emotional learning in outdoor adventure education programs.

INTRODUCTION: Many youth development programs view adolescents' process of grappling with challenges as a major driver of social-emotional learning. Our goal was to understand these processes as experienced and enacted by youth. We focused on the program Outward Bound in the United States because its students experience significant physical and social challenges and it has well-developed staff practices for facilitating learning from challenges. METHODS: Group interviews were conducted with 32 youth (ages 14-18; 50% female), immediately following their completion of Outward Bound expedition courses. Students were asked to provide a detailed narrative account of an episode on course in which they learned from challenges. Grounded theory analyses identified three processes that contributed to learning. RESULTS: First, students, described developing skills for persistence through successfully enduring distress and a process of experimenting with new mindsets that helped them rise above their anxiety and distress. Second, we found that peers provided skillful and responsive on-the-spot support that motivated youth, helped them succeed, and scaffolded students' learning strategies for dealing with physical, social, and emotional challenges. Third, we found that this peer support and scaffolding was animated by a culture of compassion and mutual commitment, which was cultivated by staff and embraced by youth. CONCLUSIONS: These findings from Outward Bound illuminate a learning model that may be useful to other youth programs. This model combines intense challenges with attuned peer support for adolescents' active processes of addressing and learning from challenges. We highlight program structures and staff practices that support these processes.

Experiencing Sampling Research from Its Beginnings into the Future.

Early experience sampling research sought to map the ecology of adolescents' lives. Its contributions include discovery of similar patterns in psychological states across diverse samples: positive emotions with friends, more negative states alone, high challenge but low motivation during schoolwork, and wider variability in teens' than adults' emotions, including more frequent extreme positive states. Recent ambulatory assessment research has expanded this mission and methods in valuable ways. Yet it still demands problem-solving (e.g., engaging participants, formulating analyses that represent teens' complex lives). A promising innovation is use of micro-longitudinal analyses to examine sequential processes (e.g., linkages between stress-coping-emotions; relationship episodes). Qualitative data can add "zones" for development of empirically-based theory about daily processes, such as adolescents' meaning-making and learning self-regulation.

Carboxyboronate: A Versatile C1 Building Block.

The synthesis and applications of carboxy-MIDA-boronate, a novel C1 building block, are described. This molecule is accessible via a ruthenium tetraoxide-mediated cleavage of commercially available ethynyl-MIDA-boronate. In the course of this study, carboxy-MIDA-boronate was found to possess ambident reactivity towards nucleophiles. Carboxylic acid derivatization produces a broad range of previously unknown carbamoyl-, oxycarbo- and thiocarboboronates. Carboxy-MIDA-boronate and its derivatives undergo condensations to access borylated heterocycles with boron at positions that are difficult to access using alternate methods. The resulting heterocycles participate in the Suzuki-Miyaura cross-coupling reaction, enabling entry into diverse bis(heteroaryl) motifs. The carbon monoxide-releasing capacity of carboxy-MIDA-boronate was also examined and applied in palladium-catalyzed carbonylation.

The important (but neglected) developmental value of roles: Findings from youth programs.

Developmental theory historically viewed demanding roles (at home, job) as important developmental contexts. However, adolescents' participation in these roles has fallen. This qualitative research examined role experiences in United States youth development programs. A central question among others was, "How can youth experience internal motivation fulfilling externally imposed role obligations?" We interviewed 73 youth with substantive work roles (e.g., Leader, Reporter, and Teacher) in 13 arts, science-technology, and leadership programs. Youth (51% female) were 14- to 18-years-old and ethnically diverse. We used grounded-theory methods suited to understanding youth's active learning processes in context. Findings illuminated youth's experiences in 4 important transactions or "steps." Youth: (a) accepted roles based on personal goals, (b) encountered difficult challenges similar to adult roles (e.g., conflicting viewpoints, role strain), (c) drew on resources to overcome challenges and fulfill role demands, and (d) learned through these experiences. Across these steps, findings suggested 3 powerful development processes. First, youth experienced multiple sources of internal motivation (e.g., agency within roles, personal and social investment, and "good pressure"), which fostered high engagement in role performance and learning. Second, experiences grappling with and fulfilling difficult role demands helped youth build important competencies for action (e.g., strategic thinking, perseverance). Third, youth's experience of accountability to others served as a powerful driver of responsibility development: Because youth were invested, they took ownership of obligations to others and learned responsive modes of thinking and acting, which they transferred to family, school, and elsewhere. We propose that teens would benefit from more opportunities for role experiences like these. (PsycINFO Database Record (c) 2019 APA, all rights reserved).

Responsibility development transfers across contexts: Reciprocal pathways between home and afterschool programs.

We investigated adolescent responsibility across 2 developmental contexts, home and an afterschool program. Longitudinal data were collected from 355 ethnically diverse 11-20-year-old adolescents (M = 15.49; 55.9% female) in 14 project-based programs. Youth rated their responsibility in the program and at home at 4 time points; parents and leaders rated youth at Time 1. The first research objective was to evaluate 3 aspects of construct validity concerning scores of responsibility assessed through a new measure. Analyses provided evidence that program- and home-responsibility scores were distinct (i.e., evidence of the structural aspect of validity); that responsibility scores were invariant across age, gender, and ethnicity (i.e., generalizability evidence); and of external validity based on parent reports (i.e., convergent evidence). The second objective was to examine cross-context transfer of responsibility. A series of cross-lagged structural equation models (SEMs) revealed that higher responsibility in each context (home, program) predicted higher responsibility in the other context, even after controlling for the stability and within-time associations. At the last time interval, the program-to-home path was significantly stronger than the corresponding home-to-program path. The third objective was to assess whether these relations were moderated by adolescent ethnicity, gender, age, or years in the program. Multigroup SEMs revealed that pathways of influence did not differ across groups. Taken as a whole, results indicate that experiences in the 2 contexts of home and program lead to interindividual differences in the development of youth self-reported responsibility, but that affordances for responsibility development across contexts change over time. (PsycINFO Database Record

Hydrogen Gas-Mediated Deoxydehydration/Hydrogenation of Sugar Acids: Catalytic Conversion of Glucarates to Adipates.

The development of a system for the operationally simple, scalable conversion of polyhydroxylated biomass into industrially relevant feedstock chemicals is described. This system includes a bimetallic Pd/Re catalyst in combination with hydrogen gas as a terminal reductant and enables the high-yielding reduction of sugar acids. This procedure has been applied to the synthesis of adipate esters, precursors for the production of Nylon-6,6, in excellent yield from biomass-derived sources.

Incidence and Predictors of Incontinence-Associated Skin Damage in Nursing Home Residents With New-Onset Incontinence.

PURPOSE: The purpose of this study was to determine the incidence and predictors of incontinence-associated dermatitis (IAD) in nursing home residents. METHODS: Records of a cohort of 10,713 elderly (≥65 years) newly incontinent nursing home residents in 448 nursing homes in 28 states free of IAD were followed up for IAD development. Potential multilevel predictors of IAD were identified in 4 national datasets containing information about the characteristics of individual nursing home residents, nursing home care environment, and communities in which the nursing homes were located. A unique set of health practitioner orders provided information about IAD and the predictors of IAD prevention and pressure injuries in the extended perineal area. Analysis was based on hierarchical logistical regression. RESULTS: The incidence of IAD was 5.5%. Significant predictors of IAD were not receiving preventive interventions for IAD, presence of a perineal pressure injury, having greater functional limitations in activities of daily living, more perfusion problems, and lesser cognitive deficits. CONCLUSION: Findings highlight the importance of prevention of IAD and treatment/prevention of pressure injuries. A WOC nurse offers expertise in these interventions and can educate staff about IAD predictors, which can improve resident outcomes. Other recommendations include implementing plans of care to improve functional status, treat perfusion problems, and provide assistance with incontinence and skin care to residents with milder as well as greater cognitive deficits.

Why Trust Matters: How Confidence in Leaders Transforms What Adolescents Gain From Youth Programs.

Youth's trust in program leaders is considered a key to the positive impact of youth programs. We sought to understand how trust influences youth's program experiences from their perspective. We interviewed 108 ethnically diverse youth (ages 12-19) participating in 13 arts, leadership, and technology programs. Analysis of these accounts suggested five ways in which youth's trust in leaders amplified program benefits. Trust increased youth's (1) confidence in leaders' guidance in program activities, (2) motivation in the program, (3) use of leaders for mentoring, (4) use of leaders as a model of a well-functioning relationship, and (5) experience of program cohesiveness. Across benefits, trust allowed youth to draw on leaders' expertise, opened them to new experiences, and helped increase youth's agency.

The Art of Restraint: How Experienced Program Leaders Use Their Authority to Support Youth Agency.

The staff of youth development programs perform a delicate balancing act between supporting youth agency and exercising necessary authority. To understand this balancing in daily practice, we interviewed 25 experienced (M = 14 years) leaders of arts, leadership, and technology programs for high-school-aged youth. We obtained accounts of when, how, and why they gave advice, set limits, and "supported youth when disagreeing." Qualitative analysis found surprising similarities across leaders. They used authority to give advice and set limits, but did so with reasoned restraint. Maximizing youth's opportunities to learn from experience was central in their decision making. They described employing authority in intentional ways aimed at helping youth's work succeed, strengthening youth's agency, and building skills for agency (e.g., critical thinking, "clarifying intent").

Total Synthesis of the Galbulimima Alkaloids Himandravine and GB17 Using Biomimetic Diels-Alder Reactions of Double Diene Precursors.

The enantioselective total syntheses of himandravine and GB17 were completed through a common biomimetic strategy involving Diels-Alder reactions of unusual double diene containing linear precursors. The double diene precursors, containing or lacking a C12 substituent as required to produce GB17 or himandravine, respectively, were found to undergo Diels-Alder reactions to afford mixtures of regioisomeric cycloadducts that map onto the alternative carbocyclic frameworks of both himandravine and GB17. Computational investigations revealed that these Diels-Alder reactions proceed via transition state structures of similar energy that have a high degree of bispericyclic character and that the low levels of regioselectivity observed in the reactions are a consequence of competing orbital interaction and distortion energies. The combined experimental and computational results provide valuable insights into the biosynthesis of the Galbulimima alkaloids.

Invited commentary: Positive youth development and human complexity.

The process of positive development for adolescents includes struggling to address a wide variety of complex, often unstated bio-psycho-social-cultural challenges. These include formulating workable values, learning self-regulation, preparation for adult work roles-and innumerable other un-tidy puzzles. Variable-based research can only scratch the surface of how youth go about these processes; nonetheless, systematic longitudinal research like this can provide valuable information about developmental pathways and directions of change. Highlights from these papers include the finding that older youth report more goals aimed at meaningful connection with others and contributing to society; yet also that moral character did not differ by age. The papers suggest that relationships adults, hope, school engagement, participation in out-of-school programs, and intentional self-regulation can serve as mediators of positive development. Yet, a striking finding was that comparatively few youth in the study manifest a pattern of change marked by the coupling of increases in positive youth development and decreases in risk/problem behavior. We believe there is much beneath the surface to be uncovered.

Adolescents' conscious processes of developing regulation: learning to appraise challenges.

To understand regulation and agency, it important to consider the nature of the regulatory challenges that adolescents must deal with. These include emotional, motivation, interpersonal, and other obstacles and problems. In this chapter, the author discusses the challenges reported by youth working on arts, technology, and social justice projects in organized programs and how they learn to address them. Adolescents' new higher-order cognitive capacities allow them to better understand the irregularities and complexity of real-world challenges. They also use these capacities to consciously develop skills to navigate these challenges.

Adolescents' development of skills for agency in youth programs: learning to think strategically.

This research examines how youth in arts and leadership programs develop skills for organizing actions over time to achieve goals. Ethnically diverse youth (ages 13-21) in 11 high-quality urban and rural programs were interviewed as they carried out projects. Qualitative analyses of 712 interviews with 108 youth yielded preliminary grounded theory about youth's development of strategic thinking, defined as use of dynamic systems reasoning to anticipate real-word scenarios and plan work. Strategic thinking appeared to develop through youth's creative engagement with tactical challenges in the work and feedback from the work's outcomes. Program advisors supported this development by giving youth control and by providing nondirective assistance when needed.

How youth get engaged: grounded-theory research on motivational development in organized youth programs.

For youth to benefit from many of the developmental opportunities provided by organized programs, they need to not only attend but become psychologically engaged in program activities. This research was aimed at formulating empirically based grounded theory on the processes through which this engagement develops. Longitudinal interviews were conducted with 100 ethnically diverse youth (ages 14­21) in 10 urban and rural arts and leadership programs. Qualitative analysis focused on narrative accounts from the 44 youth who reported experiencing a positive turning point in their motivation or engagement. For 38 of these youth, this change process involved forming a personal connection. Similar to processes suggested by self-determination theory (Ryan & Deci, 2000), forming a personal connection involved youth's progressive integration of personal goals with the goals of program activities. Youth reported developing a connection to 3 personal goals that linked the self with the activity: learning for the future, developing competence, and pursuing a purpose. The role of purpose for many youth suggests that motivational change can be driven by goals that transcend self-needs. These findings suggest that youth need not enter programs intrinsically engaged--motivation can be fostered--and that programs should be creative in helping youth explore ways to form authentic connections to program activities.

Intrinsic motivation and positive development.

Decades of scientific research shows that intrinsic motivation (IM) is a powerful "engine" of learning and positive development. This chapter synthesizes the research, first showing how the psychological state of IM is associated not only with enhanced engagement and perseverance in an activity, but also with greater use of meta-cognitive strategies and deeper processing of information. These features likely account for evidence that IM is related to greater and more effective learning. Second, we examine the determinants of this beneficial state. Evidence suggests that it results from the convergence of factors at multiple levels--from immediate conditions in the activity to longer-term personal goals, cultural values, and human dispositions. Drawing on these findings, we show that there is considerable potential for young people to develop their abilities to experience and regulate their IM within activities. In the third and final section, we then discuss how youth professionals can work with youth to help them cultivate the capacity for intrinsically motivated learning. We present ten guiding principles for cultivating IM derived from the research. We give particular attention to adolescence, because it is a period when youth become more able to engage in this deliberate cultivation--to be producers of their own development.