On the Stereochemistry of Diaryl-Substituted Cyclohexanones Formed by Michael Reactions. Trans to Cis Isomerization of Their Ketals under Basic Conditions

The stereochemistry of C-1-substituted 2,6-diphenylcyclohexan-4-ones 1−3 prepared by Michael reactions has been investigated. While preparations of these compounds have been reported over the past 70 years, in many instances the correct stereochemistry at C-2 (6) and, in some instances at C-1, was uncertain. We show here that in one case in which two identical substituents (CN) are present at C-1, it is possible to isomerize the initially formed trans isomer 1d to the cis isomer 3f. When a cyano group and a dissimilar substituent are present at C-1, the initially formed trans isomer may be isomerized to the cis compound. The stereochemistry is vertified by NMR spectroscopy and by X-ray analysis. Reaction of the ethylene ketals (4 and 5) of these ketones with KOH in DMSO at elevated temperatures gives rise to cis products, and deuterium-labeling studies demonstrated the acidity of the benzylic hydrogen at C-2 (6). Isomerization was evident since the trans ketal 4a and the cis ketal 4b gave the same amide 6a. 1H and 13C NMR spectra provided conclusive evidence for the cis → trans rearrangement

On the Stereochemistry of Diaryl-Substituted Cyclohexanones Formed by Michael Reactions. Trans to Cis Isomerization of Their Ketals under Basic Conditions

The stereochemistry of C-1-substituted 2,6-diphenylcyclohexan-4-ones 1−3 prepared by Michael reactions has been investigated. While preparations of these compounds have been reported over the past 70 years, in many instances the correct stereochemistry at C-2 (6) and, in some instances at C-1, was uncertain. We show here that in one case in which two identical substituents (CN) are present at C-1, it is possible to isomerize the initially formed trans isomer 1d to the cis isomer 3f. When a cyano group and a dissimilar substituent are present at C-1, the initially formed trans isomer may be isomerized to the cis compound. The stereochemistry is vertified by NMR spectroscopy and by X-ray analysis. Reaction of the ethylene ketals (4 and 5) of these ketones with KOH in DMSO at elevated temperatures gives rise to cis products, and deuterium-labeling studies demonstrated the acidity of the benzylic hydrogen at C-2 (6). Isomerization was evident since the trans ketal 4a and the cis ketal 4b gave the same amide 6a. 1H and 13C NMR spectra provided conclusive evidence for the cis → trans rearrangement

Navidades de Madrid y noches entretenidas: edición digital de seis novelas

Una edición digital anotada de seis novelas procedentes de la colección de Mariana de Carvajal y Saavedra, Navidades de Madrid y noches entretenidas (1663), preparada por los estudiantes de la clase SPAN 365: Escritoras y su empoderamiento en la literatura del Siglo de Oro (Gettysburg College, primavera de 2021) English: A digital annotated edition of six novels from Mariana de Carvajal y Saavedra’s collection Navidades de Madrid y noches entretenidas (1663), prepared by students in SPAN 365: Female Authors and Empowerment in Spain’s Golden Age (Gettysburg College, Spring 2021)https://cupola.gettysburg.edu/oer/1008/thumbnail.jp

The sustainability of Lean in pediatric healthcare: a realist review

Abstract Background Lean is a quality improvement management system from the Toyota manufacturing industry. Since the early 2000’s, Lean has been used as an intervention for healthcare improvement. Lean is intended to reduce costs and improve customer value through continuous improvement. Despite its extensive use, the contextual factors and mechanisms that influence the sustainability of Lean in healthcare have not been well studied. Realist synthesis is one approach to “unpack” the causal explanations of how and why Lean is sustained or not in healthcare. We conducted a realist synthesis using the context (C) + mechanim (M) = outcome (O) heuristic, to further develop and refine an initial program theory with seven CMO hypotheses, on the sustainability of Lean efforts across pediatric healthcare. Methods Our search strategy was multi-pronged, iterative, and purposeful in nature, consisting of database, gray literature, and contact with three healthcare organizations known for Lean implementation. We included primary research studies, published and unpublished case studies or reports, if they included Lean implementation with a pediatric focus and sustainability outcome. We used the Normalization Process Theory and the National Health Services Sustainability Model, an operational definition for Lean and a comprehensive definition for sustainability as guidance for data extraction and analysis. Our initial program theory with was refined using a blend of abductive and retroductive analytical processes. Results We identified six published primary research studies, two published quality improvement case studies, and three unpublished quality improvement case reports. Five CMO hypotheses from our initial program theory were substantially supported after synthesis, “sense-making and value congruency,” “staff engagement and empowerment,” and the “ripple effect” or causal pathway between Lean implementation outcomes that served as facilitating or hindering contexts for sustainability. Overall, there was variation with the conceptualization and measurement of sustainability. Conclusions This study is the first to examine Lean sustainability in pediatric healthcare using realist methods. Future research should examine whether the predictors of implementation are the same or different to sustainability and evaluate the underlying mechanisms that influence the sustainability of Lean. There is also a need for research to develop and test conceptual models and frameworks on sustainability. Systematic review registration PROSPERO-CRD42015032252