Benzothiadiazole-Based Ordered Mesoporous Polymer as a Versatile, Metal-Free Heterogeneous Photocatalyst.

Visible-light active heterogeneous organophotocatalysts have recently gained considerable interest in organic synthetic community. Ordered mesoporous polymers (OMPs) are highly promising as heterogeneous alternative to traditional precious metal/organic dyes-based photocatalysts. Herein, we report the preparation of a benzothiadiazole functionalized OMPs (BT-MPs) through a "bottom-up" strategy. High ordered periodic porosity, large surface area, excellent stability and rational energy-band structures guarantee the high catalytic activity of BT-MPs. As a result, at least six conversions, e. g., the [3+2] cycloaddition of phenols with olefins, the selective oxidation of sulfides, the C-3 thiocyanation of indole and the aminothiocyanation of ß-keto ester, could be promoted smoothly by BT-MPs. In addition, BT-MPs was readily recovered with well maintaining its photocatalytic activity and could be reused for at least eight times. This study highlights the potential of exploiting photoactive OMPs as recyclable, robust and metal-free heterogeneous photocatalysts.

Dual Proton/Silver-Catalyzed Serial (5 + 2)-Cycloaddition and Nazarov Cyclization of (E)-2-Arylidene-3-hydroxyindanones with Conjugated Eneynes: Synthesis of Indanone-Fused Benzo[cd]azulenes.

A one-pot step-economic tandem process involving (5 + 2)-cycloaddition and Nazarov cyclization reactions has been reported for the facile synthesis of indanone-fused benzo[cd]azulenes from (E)-2-arylidene-3-hydroxyindanones and conjugated eneynes. This highly regio- and stereoselective bisannulation reaction is enabled by dual silver and Brønsted acid catalysis and opens up a new avenue for the construction of important bicyclo[5.3.0]decane skeletons.

Copper-Catalyzed Oxidative Cyclization of 2-Amino-azaarenes with Lignin Models: Synthesis of 3-Phenoxy Imidazo Heterocycles.

A catalytic oxidative cyclization of 2-aminopyridines or 2-aminobenzothiazole with 2-phenoxyacetophenones (a kind of lignin platform compound) was developed, efficiently providing valuable 3-phenoxy imidazo[1,2-a]pyridines or 3-phenoxy benzo[d]imidazo[2,1-b]thiazoles. The reaction was realized under oxygen by simply using inexpensive CuI as the catalyst.

Asymmetric Total Syntheses of ent-Stachybotrin C and Its Congener.

The asymmetric total syntheses of ent-stachybotrin C and its congener have been accomplished through a convergent approach in the longest linear sequence of 12 steps from commercially available materials, respectively. Noteworthy transformation of the synthesis involved a cascade Knoevenagel condensation/Hantzsch ester reduction/epoxide ring-opening/transetherification to construct the core pyran ring with two adjacent stereocenters.

Influence of Nurse-Led Health Education on Self-Management Ability, Satisfaction, and Compliance of Elderly Patients with Chronic Obstructive Pulmonary Disease Based on Knowledge, Belief, and Practice Model.

Objective: Knowledge, belief, and behavior model (knowledge-attitude-practice (KAP)) is known as a cognitive model. Health education is important to the prognosis of patients, including chronic obstructive pulmonary disease (COPD) patients. However, the investigation regarding health education based on the KAP model is few. Thus, this work is aimed at analyzing the influence of nurse-led health education on self-management ability, satisfaction, and compliance of elderly patients with COPD based on knowledge, belief, and practice model. Methods: 60 elderly patients with COPD cured in our hospital from January 2019 to April 2021 were enrolled for the study. The patients were randomly assigned to control group (n = 30) and study group (n = 30). The former group received routine nursing, and the latter group accepted health education based on "knowledge, belief, and practice" model. Finally, the scores of nursing satisfaction, KAP score, compliance rate, self-management level, pulmonary function, and life quality were compared in the two groups. Results: The nursing satisfaction of the study group (100.00%) was higher than that (83.33%) of the control group (P < 0.05). The scores of knowledge, attitude, and behavior were remarkably higher in the study group than in the control group after nursing (P < 0.05). Moreover, KAP scores also significantly increased in the study group after nursing. The compliance rate of the study group (93.33%) was higher than that of the control group (66.67%) (P < 0.05). After nursing, the scores of symptom management, daily life management, emotion management, information management, and management efficiency were higher in the study group than in the control group (P < 0.05). In addition, pulmonary functions were improved in the two groups following nursing. Compared with the control groups, the 6 min walking distance, FEV1%, and FEV1/FVC% were higher in the study group (P < 0.05). After nursing, the scores of life quality were reduced in the two groups. The scores of physiological function, psychological function, social function, and health self-cognition were lower in the study group than in the control group (P < 0.05). Conclusion: Based on the model of knowledge, belief, and practice, nurse-led health education can successfully enhance the self-management ability, satisfaction, and compliance of elderly COPD patients.

Cobalt-Catalyzed Olefinic C-H Alkenylation/Alkylation Switched by Carbonyl Groups.

The first cobalt-catalyzed cross-couplings between olefins has been demonstrated to provide C(alkenyl)-H alkenylation and alkylation products, using complex [Cp*Co(CO)I2]. While coupling partner acrylates afforded conjugated dienoates, α,ß-unsaturated ketones led to γ-alkenyl ketones completely, representing a switchable C-H functionalization controlled by different carbonyl groups.

Geminal group-directed olefinic C-H functionalization via four- to eight-membered exo-metallocycles.

Great efforts have been made in the activation of a C(alkenyl)-H bond vicinal to the directing group to proceed via five- or six-membered endo-metallocycles. In stark contrast, functionalization of a C(alkenyl)-H bond geminal to the directing group via exo-metallocycle pathway continued to be elusive. Here we report the selective transformation of an olefinic C-H bond that is geminal to the directing group bearing valuable hydroxyl, carbamate or amide into a C-C bond, which proceeds through four- to eight-membered exo-palladacycles. Compared to the reported mechanisms proceeding only through six-membered exo-palladacycles via N,N-bidentate chelation, our weak and O-monodentate chelation-assisted C(alkenyl)-H activations tolerate longer or shorter distances between the olefinic C-H bonds and the coordinating groups, allowing for the functionalizations of many olefinic C-H bonds in alkenyl alcohols, carbamates and amides. The synthetic applicability has been demonstrated by the preparative scale and late-stage C-H functionalization of steroid and ricinoleate derivatives.

Acylsilane directed aromatic C-H alkenylations by ruthenium catalysis.

A ruthenium-catalyzed C-H alkenylation of aroylsilanes with electron-deficient alkenes was developed, using acylsilane as the directing group. The mild reaction conditions enable the tolerance of a wide scope of functionalities such as OMe, F, Cl, Br and CF3, providing a convenient and highly effective method for the synthesis of styrene derivatives bearing acylsilane. Steroid and heterocycles such as furan and thiophene were also well tolerated. Furthermore, acylsilane was efficiently converted to the corresponding aldehyde or carboxylic acid.

Iridium-catalyzed alkenyl C-H allylation using conjugated dienes.

An iridium-catalyzed C-H allylation of acrylamides with conjugated dienes was developed, using NH-Ts amide as the directing group. The ligand- and additive-free protocol provided a convenient and atom economic synthesis of branched 1,4-diene skeletons, enabling the tolerance of a wide scope of functionalities such as OMe, F, Cl, Br and CF3. The utility of this protocol is also demonstrated by a preparative scale, as well as C-H functionalization of artemisic amide. Furthermore, NH-Ts amide was efficiently removed by methylation and hydrolysis procedures to provide 1,4-dienoic acid.

Ruthenium-catalyzed olefinic C-H alkenylation of enol-carbamates: highly stereo-selective synthesis of (Z,Z) and (Z,E)-butadienes.

Cross-coupling reactions of enol carbamates with alkynes or alkenes are reported, using an inexpensive ruthenium catalyst. With the assistance of the directing group OCONMe2, the protocols provide mild, stereo-selective and efficient routes for the preparation of valuable (Z,Z) and (Z,E)-butadiene skeletons.