Photoinduced Deaminative Alkylation for the Synthesis of γ-Ketoesters via Electron Donor-Acceptor Complex Formation.

Visible-light-induced deaminative alkylation of Katritzky salts with silyl enol ethers has been developed. The reaction can proceed efficiently through electron donor-acceptor complex formation, avoiding the use of precious metal complexes or synthetically elaborate organic dyes. A series of functionalized γ-ketoesters was successfully obtained with good functional group tolerance and compatibility under mild and straightforward conditions.

Efficient Pd-Catalyzed Regio- and Stereoselective Carboxylation of Allylic Alcohols with Formic Acid.

Formic acid is efficiently used as a C1 source to directly carboxylate allylic alcohols in the presence of a low loading of palladium catalyst and acetic anhydride as additive to afford ß,γ-unsaturated carboxylic acids with excellent chemo-, regio-, and stereoselectivity. The reaction proceeds through a carbonylation process with in situ-generated carbon monoxide under mild conditions, avoiding the use of high-pressure gaseous CO. A bisphosphine ligand with a large bite angle (4,5-bis{diphenylphosphino}-9,9-dimethylxanthene, Xantphos) was found to be uniquely effective for this transformation. The regio- and stereoconvergence of this reaction is ascribed to the thermodynamically favored isomerization of the allylic electrophile in the presence of the palladium catalyst.

Photoredox-Catalysed Decarboxylative Alkylation of N-Heteroarenes with N-(Acyloxy)phthalimides.

An iridium photoredox catalyst in combination with either a stoichiometric amount of Brønsted acid or a catalytic amount of Lewis acid is capable of catalyzing regioselective alkylation of N-heteroarenes with N-(acyloxy)phthalimides at room temperature under irradiation. A broad range of N-heteroarenes can be alkylated using a variety of secondary, tertiary, and quaternary carboxylates. Mechanistic studies suggest that an IrII /IrIII redox catalytic cycle is responsible for the observed reactivity.

Mechanism of Boron-Catalyzed N-Alkylation of Amines with Carboxylic Acids.

Mechanistic study has been carried out on the B(C6F5)3-catalyzed amine alkylation with carboxylic acid. The reaction includes acid-amine condensation and amide reduction steps. In condensation step, the catalyst-free mechanism is found to be more favorable than the B(C6F5)3-catalyzed mechanism, because the automatic formation of the stable B(C6F5)3-amine complex deactivates the catalyst in the latter case. Meanwhile, the catalyst-free condensation is constituted by nucleophilic attack and the indirect H2O-elimination (with acid acting as proton shuttle) steps. After that, the amide reduction undergoes a Lewis acid (B(C6F5)3)-catalyzed mechanism rather than a Brønsted acid (B(C6F5)3-coordinated HCOOH)-catalyzed one. The B(C6F5)3)-catalyzed reduction includes twice silyl-hydride transfer steps, while the first silyl transfer is the rate-determining step of the overall alkylation catalytic cycle. The above condensation-reduction mechanism is supported by control experiments (on both temperature and substrates). Meanwhile, the predicted chemoselectivity is consistent with the predominant formation of the alkylation product (over disilyl acetal product).

Boron-Catalyzed N-Alkylation of Amines using Carboxylic Acids.

A boron-based catalyst was found to catalyze the straightforward alkylation of amines with readily available carboxylic acids in the presence of silane as the reducing agent. Various types of primary and secondary amines can be smoothly alkylated with good selectivity and good functional-group compatibility. This metal-free amine alkylation was successfully applied to the synthesis of three commercial medicinal compounds, Butenafine, Cinacalcet. and Piribedil, in a one-pot manner without using any metal catalysts.

Beyond person-environment congruence: Career adaptability, career personality styles, and thinking styles.

The main objectives of this study were to explore the relationship between career personality styles and career adaptability and the role of thinking styles in such relationship. Eight hundred and eleven Chinese students, who were trained as pre-service kindergarten teachers, responded to the Career Personality Styles Inventory, the shortened Thinking Styles Inventory-Revised, and the Career Adapt-Ability Scale - Short Form. Results suggested that the career personality styles (i.e. social, enterprising) that fit the vocational environment of kindergarten teaching the most positively predicted the students' career adaptability, both directly and indirectly through creativity-generating thinking styles. Moreover, the artistic and investigative career personality styles indirectly predicted students' career adaptability through creativity-generating thinking styles, while the conventional and realistic career personality styles showed no significant effect on the students' career adaptability. The findings imply that beyond the notion of person-environment congruence, some career personality styles can consistently predict career adaptability through thinking styles. Implications for career counseling and education practice are discussed.

Photoinduced Triphenylphosphine and Iodide Salt Promoted Reductive Decarboxylative Coupling.

The transient electron donor-acceptor (EDA) complex has been an emerging area in the photoinduced organic synthesis field, generating radicals without exogenous transition-metal or organic dye-based photoredox catalysts. The catalytic platform to form suitable photoactive EDA complexes for photochemical reduction reactions remains underdeveloped. Herein, a general photoinduced reductive alkylation via the EDA complex strategy is described. A simple yet multifunctional system, triphenylphosphine and iodide salt, promotes the photoinduced decarboxylative hydroalkylation, and reductive defluorinative decarboxylative alkylation of trifluoromethyl alkenes, to access trifluoromethyl alkanes and gem-difluoroalkenes. Moreover, decarboxylative hydroalkylation can be applied to more kinds of electron-deficient alkenes as a general Giese addition reaction.

Understanding beginning teachers' professional identity changes through job demands-resources theory.

Teachers' professional identity is malleable. However, changes in first-year teachers' professional identity are under-documented in the literature. This study attempted to understand these changes using the job demands-resources (JD-R) model in the context of a two-wave investigation before and after the first year of teaching (Time 1 and Time 2). A total of 464 elementary and secondary schoolteachers reported twice their perceived professional identity in terms of job satisfaction, occupational commitment, teacher self-efficacy, and motivation to teach. School characteristics were captured in terms of job demands and job resources at T2. Findings estimated by the rank-order change, the mean-level change, and the Reliable Change Index indicated significant declines in these teachers' professional identity over one year. Autoregressive change analysis revealed that growth opportunities (job resources) and emotional demands (job demands) in the school context played a major role in the observed declines. Suggestions and implications are discussed for key stakeholders of teacher education programs and teachers' professional development.

The Relationships Between Career-Related Emotional Support From Parents and Teachers and Career Adaptability.

Career-related support from parents and teachers plays an essential role in the process of promoting young people's career development. This study examined the relationship between parents' and teachers' career-related support and career adaptability among Chinese male primary school preservice teachers (N = 772). The participants completed the Career Adapt-Abilities Scale-Short Version (CAAS), the Career-Related Parental Support Scale (CRPSS), and the Career-Related Teacher Support Scale (CRTSS). Results showed that a high level of emotional support from parents and teachers had more effects on the career adaptability of Chinese male primary school preservice teachers then other aspects in the scale, and teachers' emotional support is more important than parents' emotional support. Notably, there is a complex correlation among education level and occupation of parents and their children's occupational adaptability. These findings carry implications for supporting teachers and parents in facilitating preservice teachers' career adaptability. Future research could identify the differential effects of different forms of teacher support and parental support relate to career adaptability.

Photoredox-Catalyzed Allylic Defluorinative Alkoxycarbonylation of Trifluoromethyl Alkenes through Intermolecular Alkoxycarbonyl Radical Addition.

The gem-difluoroalkene moiety is an ideal carbonyl bioisostere in medicinal chemistry, but efficient synthesis of ß-gem-difluoroalkene esters remains challenging so far. Herein, we disclose a photoredox-catalyzed allylic defluorinative alkoxycarbonylation of trifluoromethyl alkenes enabled by intermolecular alkoxycarbonyl radical addition. A wide variety of alcohol oxalate derivatives were amenable, affording various ß-gem-difluoroalkene esters with excellent functional group tolerance. Notably, the potential synthetic value of this method is highlighted by successful late-stage modification for bioactive molecules.

Transition-metal-free decarboxylative thiolation of stable aliphatic carboxylates.

A transition-metal-free decarboxylative thiolation protocol is reported in which primary, secondary, tertiary (hetero)aryl acetates and α-CN substituted acetates undergo the decarboxylative thiolation smoothly, to deliver a variety of functionalized aryl alkyl sulfides in moderate to excellent yields. Aryl diselenides are also amenable substrates for construction of C-Se bonds under the simple and mild reaction conditions. Moreover, the protocol is successfully applied to the late-stage modification of pharmaceutical carboxylates with satisfactory chemoselectivity and functional-group compatibility.

Triphenylphosphine-Catalyzed Alkylative Iododecarboxylation with Lithium Iodide under Visible Light.

Under irradiation of 456 nm blue light-emitting diodes, PPh3 catalyzes the iododecarboxylation of aliphatic carboxylic acid derived N-(acyloxy)phthalimide with lithium iodide as an iodine source. The reaction delivers primary, secondary, and bridgehead tertiary alkyl iodides in acetone solvent, and the alkyl iodide products were easily used to generate C-N, C-O, C-F, and C-S bonds to allow various decarboxylative transformations without using transition-metal or organic-dye-based photocatalysts.

Nickel-catalyzed carboxylation of aryl iodides with lithium formate through catalytic CO recycling.

A protocol for the Ni-catalyzed carboxylation of aryl iodides with formate has been developed with good functional group compatibility for the synthesis of a variety of aromatic carboxylic acids under mild conditions. The reaction tolerates other functionalities for cross-coupling, such as aryl bromide, aryl chloride, aryl tosylate, and aryl pinacol boronate. The reaction proceeds through a carbonylation process with in situ generated carbon monoxide in the presence of a catalytic amount of acetic anhydride and lithium formate, avoiding the use of gaseous CO. The strategy of CO recycling in catalytic amounts is critical for the success of the reaction.

Photocatalytic decarboxylative alkenylation of α-amino and α-hydroxy acid-derived redox active esters by NaI/PPh3 catalysis.

Herein, we report the photocatalytic decarboxylative alkenylation reactions of N-(acyloxy)phthalimide derived from α-amino and α-hydroxy acids with 1,1-diarylethene, and with cinnamic acid derivatives through double decarboxylation, using sodium iodide and triphenylphosphine as redox catalysts. The reaction proceeds under mild irradiation conditions with visible blue light (440 nm or 456 nm) in an acetone solvent without recourse to transition-metal or organic dye based photoredox catalysts. The reaction proceeds via photoactivation of a transiently self-assembled chromophore from N-(acyloxy)phthalimide and NaI/PPh3. Solvation plays a crucial role in the reactivity.

Photocatalytic decarboxylative alkylations mediated by triphenylphosphine and sodium iodide.

Most photoredox catalysts in current use are precious metal complexes or synthetically elaborate organic dyes, the cost of which can impede their application for large-scale industrial processes. We found that a combination of triphenylphosphine and sodium iodide under 456-nanometer irradiation by blue light-emitting diodes can catalyze the alkylation of silyl enol ethers by decarboxylative coupling with redox-active esters in the absence of transition metals. Deaminative alkylation using Katritzky's N-alkylpyridinium salts and trifluoromethylation using Togni's reagent are also demonstrated. Moreover, the phosphine/iodide-based photoredox system catalyzes Minisci-type alkylation of N-heterocycles and can operate in tandem with chiral phosphoric acids to achieve high enantioselectivity in this reaction.

How Is Learning Motivation Shaped Under Different Contexts: An Ethnographic Study in the Changes of Adult Learner's Motivational Beliefs and Behaviors Within a Foreign Language Course.

There has been a burgeoning interest of students' motivational beliefs in determining their motivational behaviors in classroom activities: choice of task and persistence of task. Previous research mostly used quantitative methods to understand students' general motivation, without taking contextual factors into consideration. To fill in this gap, the present study examined the influence of changing contexts on students' motivational beliefs in a Chinese language classroom, and how those changes in motivational beliefs shaped their motivational behaviors in class activities. An ethnographic multiple-case study approach was adopted, and six adult learners were chosen from a Chinese language course in a Hong Kong university. On-going semi-structured interviews, class observations, stimulated recall and document reviews were conducted to understand student development across time. Findings show that the more proficient students were showing relatively stable motivational beliefs as well as behaviors throughout the foreign language course. In contrast, the less proficient students were demonstrating obvious changes in their motivational beliefs and hence behaviors, due to the different contexts of non-exam and high-stake exam. The study suggested students' learning motivation in class was context-dependent, and could fluctuate substantially on a weekly basis. Those dynamic within-course changes at different learning stages and the reasons shaping the changes could give pedagogical insights to the teacher with adult learners.

Parental absence predicts suicide ideation through emotional disorders.

The objectives of the study were to investigate the association between the parental absence and suicide ideation and to examine the roles of emotional disorders in the aforementioned relationship. Four thousand five hundred and thirteen children from rural areas in Jiangsu Province, China, participated in the study. Among the participants, 2416 were non-left-behind children (children living with both parents) and 1997 were left-behind children (children living with the absence of at least one parent). All participants responded to the Center for Epidemiological Studies Depression Scale for Children, the Multidimensional Anxiety Scale for Children, and a question regarding respondents' suicide ideation. Results indicated that as compared with non-left-behind children, the left-behind children with both-parents absence were statistically more likely to show suicide ideation. Furthermore, all the three types parental absence-father absence, mother absence, and both-parents absence were significantly associated with negative emotional outcomes. Moreover, depression, social anxiety, and physical anxiety were shown to be significant mediators in the relationship of parental absence and suicide ideation of children. The stress of parental absence and its negative impact on children's mental health are discussed.

Remembering the Leaders of China.

In two studies, we examined Chinese students' memory for the names of the leaders of China. In Study 1, subjects were cued with the names of periods from China's history. Subjects listed as many leaders as possible from each period and put them in the correct ordinal position when they could (see Roediger and DeSoto, 2014). Results showed that within each period, a primacy effect and sometimes a recency effect emerged. Moreover, the average recall probability for leaders within a specific period was a function of the ordinal position of the period. In Study 2, we asked another group of subjects to identify the sources through which they were able to recall each leader. We found that most subjects remembered leaders due to class and coursework. We also found a relation between a leader's recall probability and the amount of information available on that leader on the Internet. Our findings further imply that the serial position function captures the form of collective memory.

The Scope and Trends of Pediatric Hospitalizations in Texas, 2004-2010.

OBJECTIVE: To examine demographics and trends of financial cost and prominent diseases/conditions resulting in inpatient hospitalizations for infants, children, and adolescents in Texas between 2004 and 2010. METHODS: Longitudinal retrospective cross-sectional study using the Texas Hospital Inpatient Discharge Database, including all pediatric hospitalizations in the state of Texas, 2004 to 2010. RESULTS: Texas has an average of 591 571 pediatric hospitalizations per year. Birth was the most common reason for hospitalization, representing 64% of all pediatric hospitalization annually in Texas. Respiratory illnesses were the most common discharge diagnosis for hospitalized children ages 1 month to 9 years and demonstrated a 2% decrease over the study period. The rate of hospitalizations for digestive conditions and childbirth also demonstrated a decrease over this time frame: 4.7% and 3.0%, respectively. The rate of mental illness diagnoses increased 2.5% over the time frame and represented the most common discharge diagnosis for children aged 10 to 14. Childbirth was the most common reason for hospitalization for adolescents aged 15 to 17 years. There was no increase in total cost of pediatric hospitalizations over the time period under study. CONCLUSIONS: After birth, respiratory illnesses represent the most common reason for hospitalization for children (between 1 month and 10 years of age) in Texas. Mental health conditions and childbirth represent the most common reason for hospitalization for young adolescents (10-14 years) and older adolescents (15-17 years), respectively.