Density functional theory calculations have been performed to investigate the palladium‐catalyzed remote diborylative cyclization of dienes. The computations reveal that the reaction proceeds through a rarely explored Pd(II)/Pd(IV) catalytic cycle, and the formal σ‐bond metathesis between the alkylpalladium intermediate and B2pin2 occurs via the pathway of the B−B oxidative addition/C−B reductive elimination involving the high‐valent Pd(IV) species. The diastereoselectivity is determined by the migratory insertion into the Pd−C bond, which is mainly due to the combination of the torsional strain effect, steric repulsion and C−H—O hydrogen‐bonding interaction. The steric hindrance around the reacting carbon group in the C−B reductive elimination turns out to be a key factor to provide the driving force of the chain walking of the Pd center to the terminal primary carbon position, enabling the experimentally observed remote regioselectivity.

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Background. Sleep disturbances and benzodiazepine (BZD)/Z-drug use are common in patients with bipolar disorder (BD). Objective. To investigate the short- and long-term effects of BZD/Z-drug use during acute affective episode. Methods. Participants diagnosed with BD as well as sleep disturbance chose BZDs/Z-drugs or not at will. Manic and depressive symptoms were assessed by Mental Disorders Questionnaire (MDQ) and Quick Inventory of Depressive Symptoms (QIDS) as self-reporting surveys. The participants were assessed by trained evaluators at baseline and months 1, 3, 6, and 9. Results. 61 patients with BD combined sleep disturbances were studied. At baseline, patients who used BZDs/Z-drugs had more amount of mood stabilizers ( p = 0.038 ), other psychotropic medications ( p = 0.040 ), and more risk of suicide attempt ( p = 0.019 ). The BZD/Z-drug group had a significantly higher QIDS reductive ratio as compared with the no BZD/Z-drug group at month 1; no significant differences in the variability of MDQ, QIDS reductive ratio, or recurrence rate were found between these two groups at baseline, month 1, month 3, month 6, or month 9. Conclusions. During acute affective episode, patients with BD combined sleep disturbance who took BZDs/Z-drugs tended to use more amount of mood stabilizers. Polytherapy of BZDs/Z-drugs or other psychiatric drugs could increase suicide attempt during an acute affective episode. BZD/Z-drug use, however, had a significant effect on helping depressive symptoms alleviate during affective period.