Mechanistic Details of Asymmetric Bromocyclization with BINAP Monoxide: Identification of Chiral Proton-Bridged Bisphosphine Oxide Complex and Its Application to Parallel Kinetic Resolution.

The mechanism of our previously reported catalytic asymmetric bromocyclization reactions using 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP) monoxide was examined in detail by the means of control experiments, NMR studies, X-ray structure analysis, and CryoSpray electrospray ionization mass spectrometry (ESI-MS) analysis. The chiral BINAP monoxide was transformed to a key catalyst precursor, proton-bridged bisphosphine oxide complex (POHOP·Br), in the presence of N-bromosuccinimide (NBS) and contaminating water. The thus-formed POHOP further reacts with NBS to afford BINAP dioxide and molecular bromine (Br2) simultaneously in equimolar amounts. While the resulting Br2 is activated by NBS to form a more reactive brominating reagent (Br2─NBS), BINAP dioxide serves as a bifunctional catalyst, acting as both a Lewis base that reacts with Br2─NBS to form a chiral brominating agent (P═O+─Br) and also as a Brønsted base for the activation of the substrate. By taking advantage of this novel concerted Lewis/Brønsted base catalysis by BINAP dioxide, we achieved the first regio- and chemodivergent parallel kinetic resolutions (PKRs) of racemic unsymmetrical bisallylic amides via bromocyclization.

Large Questionnaire Survey on Sleep Duration and Insomnia Using the TV Hybridcast System by Japan Broadcasting Corporation (NHK).

BACKGROUND: Japanese people are known to have the shortest sleep duration in the world. To date, no study has assessed a large Japanese population for insomnia and sleep duration. METHODS: We performed an Ιnternet-based survey in association with a national television (TV) program. Questionnaire data were collected not only through personal computers, tablets, and smartphones, but also through the Hybridcast system, which combines broadcasts over airwaves with broadband data provided via the Internet using the TV remote controller. The Athens Insomnia Scale (AIS) was used to assess insomnia. RESULTS: A total of 301,241 subjects participated in the survey. Participants slept for an average of 5.96 ± 1.13 h; the average AIS score was 6.82 ± 3.69. A total of 26.1% of male and 27.1% of female participants had both insomnia (AIS ≥ 6) and short sleep duration (<6 h). Responses were recorded through the Hybridcast system for 76.4% of the elderly (age ≥ 65 years) subjects and through personal computers, tablets, or smartphones for 59.9-82.7% of the younger subjects (age ≤ 65 years). CONCLUSIONS: Almost a quarter of the Japanese participants presented short sleep duration and insomnia. Furthermore, the Hybridcast system may be useful for performing large internet-based surveys, especially for elderly individuals.

Assessing the quality of cancer screening leaflets using the International Patient Decision Aids Standards instrument: A cross-sectional content analysis.

OBJECTIVE: To assess the quality of national cancer screening program leaflets in Japan from the informed-decision perspective. METHODS: Cross-sectional content analysis of invitation leaflets issued by centralized organizations and used nationwide in Japan was conducted. Three members independently evaluated the materials using International Patient Decision Aids Standards six-item minimum criteria for qualifying patient decision aids. PATIENT PUBLIC INVOLVEMENT: Co-author KH is a cancer patient himself. We also sought feedbacks from three other cancer survivors and two bereaved family members. RESULTS: Inter-rater agreement was substantial (Fleiss' kappa=0.62). The median score was 2 out of 6 (range: 2-3). All leaflets described the cancer (Q1: 7/7) and screening modality (Q2: 7/7). None stated not undergoing screening as an option. One stated another screening modality (Q3: 1/7). None stated both the positive and negative features of multiple options (Q4: 0/7. Q5: 0/7). One described the psychological and social experience of screening but only its positive side (Q6: 1/7). CONCLUSIONS: There is room for improvement in the content of the public cancer screening invitation leaflets in Japan from informed-decision perspective. PRACTICE IMPLICATIONS: Cancer screening leaflets should provide evidence-based, well-balanced, easy-to-understand information to educate people on cancer screening while maintaining people's autonomy.