Catalytic Asymmetric Hydroalkoxylation and Formal Hydration and Hydroaminoxylation of Conjugated Dienes.

The straightforward construction of stereogenic centers bearing unprotected functional groups, as in nature, has been a persistent pursuit in synthetic chemistry. Abundant applications of free enantioenriched allyl alcohol and allyl hydroxylamine motifs have made the asymmetric hydration and hydroaminoxylation of conjugated dienes from water and hydroxylamine, respectively, intriguing and efficient routes that have, however, been unachievable thus far. A fundamental challenge is the failure to realize transition-metal-catalyzed enantioselective C-O bond constructions via hydrofunctionalization of conjugated dienes. Here, we perform a comprehensive study toward the stereoselective formal hydration and hydroaminoxylation of conjugated dienes by synthesizing a set of new P,N-ligands and identifying an aryl-derived oxime as a surrogate for both water and hydroxylamine. Asymmetric hydroalkoxylation with new P,N-ligands is also elucidated. Furthermore, versatile derivatizations following hydration provide indirect but concise routes to formal hydrophenoxylation, hydrofluoroalkoxylation, and hydrocarboxylation of conjugated dienes that have been unreported thus far. Finally, a ligand-to-ligand hydrogen transfer process is proposed based on the results of preliminary mechanistic experiments.

Evaluation of a culturally adapted cognitive behavior therapy-based, third-wave therapy manual.

BACKGROUND: Recommendations for psychotherapy have evolved over the years, with cognitive behavioral therapy (CBT) taking precedence since its inception within clinical guidelines in the United Kingdom and United States. The use of CBT for severe mental illness is now more common globally. AIM: To investigate the feasibility and acceptability of a culturally adapted, CBT-based, third-wave therapy manual using the Comprehend, Cope, and Connect approach with individuals from a diverse population presenting to primary and secondary healthcare services. METHODS: A pilot study was used to assess the feasibility and acceptability of the manualised intervention. Outcome measures were evaluated at baseline, post-intervention and 12 wk-follow up. 32 participants with mental health conditions aged 20-53 years were recruited. Assessments were completed at three time points, using Clinical Outcomes in Routine Evaluation (CORE), Hospital Anxiety and Depression Scale (HADS), Bradford Somatic Inventory and World Health Organization Disability Assessment Schedule 2.0 (WHODAS). The Patient Experience Ques-tionnaire was completed post-treatment. RESULTS: Repeated measures of analysis of variance associated with HADS depression, F (2, 36) = 12.81, P < 0.001, partial η2 = 0.42 and HADS anxiety scores, F (2, 26) = 9.93, P < 0.001, partial η2 = 0.36; CORE total score and WHODAS both showed significant effect F (1.25, 18.72) = 14.98, P < 0.001, partial η2 = 0.5. and F (1.29, 14.18) = 6.73, P < 0.001, partial η2 = 0.38 respectively. CONCLUSION: These results indicate the effectiveness and acceptability of the culturally adapted, CBT-based, third-wave therapy manual intervention among minoritized groups with moderate effect sizes. Satisfaction levels and acceptability were highly rated. The viability and cost-effectiveness of this approach should be explored further to support universal implementation across healthcare systems.