A Sterically Tuned Directing Auxiliary Promotes Catalytic 1,2-Carbofluorination of Alkenyl Carbonyl Compounds.

The site-selective palladium-catalyzed three-component coupling of unactivated alkenyl carbonyl compounds, aryl- or alkenylboronic acids, and N-fluorobenzenesulfonimide is described herein. Tuning of the steric environment on the bidentate directing auxiliary enhances regioselectivity and facilitates challenging C(sp3 )-F reductive elimination from a PdIV intermediate to afford 1,2-carbofluorination products in moderate to good yields.

Structurally Diverse Bench-Stable Nickel(0) Pre-Catalysts: A Practical Toolkit for In Situ Ligation Protocols.

A flurry of recent research has centered on harnessing the power of nickel catalysis in organic synthesis. These efforts have been bolstered by contemporaneous development of well-defined nickel (pre)catalysts with diverse structure and reactivity. In this report, we present ten different bench-stable, 18-electron, formally zero-valent nickel-olefin complexes that are competent pre-catalysts in various reactions. Our investigation includes preparations of novel, bench-stable Ni(COD)(L) complexes (COD=1,5-cyclooctadiene), in which L=quinone, cyclopentadienone, thiophene-S-oxide, and fulvene. Characterization by NMR, IR, single-crystal X-ray diffraction, cyclic voltammetry, thermogravimetric analysis, and natural bond orbital analysis sheds light on the structure, bonding, and properties of these complexes. Applications in an assortment of nickel-catalyzed reactions underscore the complementary nature of the different pre-catalysts within this toolkit.

Nickel-Catalyzed 1,2-Carboamination of Alkenyl Alcohols.

An alcohol-directed, nickel-catalyzed three-component umpolung carboamination of unactivated alkenes with aryl/alkenylboronic esters and electrophilic aminating reagents is reported. This transformation is enabled by specifically tailored O-(2,6-dimethoxybenzoyl)hydroxylamine electrophiles that suppress competitive processes, including undesired ß-hydride elimination and transesterification between the alcohol substrate and electrophile. The reaction delivers the desired 1,2-carboaminated products with generally high regio- and syn-diastereoselectivity and exhibits a broad scope of coupling partners and alkenes, including complex natural products. Various mechanistic experiments and analysis of the stereochemical outcome with a cyclic alkene substrate, as confirmed by X-ray crystallographic analysis, support alcohol-directed syn-insertion of an organonickel(I) species.

Synthesis, Characterization, and Reactivity of Cationic Gold Diarylallenylidene Complexes.

Methoxide abstraction from gold acetylide complexes of the form (L)Au[η1 -C≡CC(OMe)ArAr'] (L=IPr, P(t Bu)2 (ortho-biphenyl); Ar/Ar'=C6 H4 X where X=H, Cl, Me, OMe) with trimethylsilyl trifluoromethanesulfonate (TMSOTf) at -78 °C resulted in the formation of the corresponding cationic gold diarylallenylidene complexes [(L)Au=C=C=CArAr']+ OTf- in ≥85±5 % yield according to 1 H NMR analysis. 13 C NMR and IR spectroscopic analysis of these complexes established the arene-dependent delocalization of positive charge on both the C1 and C3 allenylidene carbon atoms. The diphenylallenylidene complex [(IPr)Au=C=C=CPh2 ]+ OTf- reacted with heteroatom nucleophiles at the allenylidene C1 and/or C3 carbon atom.

Regulation of diastereoselectivity in the carbocyclization of allenyl (S)-N-tert-butylsulfinimines through a three-component assembly.

Allenyl sulfinimines can be stereoselectively cyclized with hexamethylditin under palladium catalysis conditions followed by a selection of additives for an activated transmetalation. Reactivity and diastereoselectivity for the cyclization strongly depend on the characteristics of additives. A highly diastereoselective synthesis of five-membered rings is achieved from the reaction of the corresponding allenyl (S)-N-tert-butylsulfinimies through the following sequence. After the distannylation of the allenyl group with hexamethylditin catalyzed by the Pd complex, stereochemical routes are additive dependent: addition of SnCl4 affords a cis ring exclusively, whereas a trans ring is formed predominantly by the introduction of B-bromocatecholborane. Extension of the methodology to the synthesis of six-membered cis rings is achieved by using B-bromocatecholborane. Stereochemical relationships of products were unambiguously deduced by X-ray crystallography.

Conditional Dependence across Slow and Fast Item Responses: With a Latent Space Item Response Modeling Approach.

There recently have been many studies examining conditional dependence between response accuracy and response times in cognitive tests. While most previous research has focused on revealing a general pattern of conditional dependence for all respondents and items, it is plausible that the pattern may vary across respondents and items. In this paper, we attend to its potential heterogeneity and examine the item and person specificities involved in the conditional dependence between item responses and response times. To this end, we use a latent space item response theory (LSIRT) approach with an interaction map that visualizes conditional dependence in response data in the form of item-respondent interactions. We incorporate response time information into the interaction map by applying LSIRT models to slow and fast item responses. Through empirical illustrations with three cognitive test datasets, we confirm the presence and patterns of conditional dependence between item responses and response times, a result consistent with previous studies. Our results further illustrate the heterogeneity in the conditional dependence across respondents, which provides insights into understanding individuals' underlying item-solving processes in cognitive tests. Some practical implications of the results and the use of interaction maps in cognitive tests are discussed.

Noncompensatory MIRT For Passage-Based Tests.

We consider a multidimensional noncompensatory approach for binary items in passage-based tests. The passage-based noncompensatory model (PB-NM) emphasizes two underlying components in solving passage-based test items: a passage-related component and a passage-independent component. An advantage of the PB-NM model over commonly applied compensatory models (e.g., bifactor model) is that the two components are parameterized in relation to difficulty as opposed to discrimination parameters. As a result, while simultaneously accounting for passage-related local item dependence, the model permits the assessment of how items based on the same passage may require varying levels of passage comprehension (as well as varying levels of passage-independent proficiency) to obtain a correct response. Through a simulation study, we evaluate the comparative fit of the PB-NM against the bifactor model and also illustrate the relationship between the difficulty parameters of the PB-NM and the discrimination parameters of the bifactor model. We further apply the PB-NM to an actual reading comprehension test to demonstrate the relevance of the model in understanding variation in the relative difficulty of the two components across different item types.

(CAAC)Copper Catalysis Enables Regioselective Three-Component Carboboration of Terminal Alkynes.

Cyclic(alkyl)(amino)carbene (CAAC) ligands are found to perturb regioselectivity of the copper-catalyzed carboboration of terminal alkynes, favoring the less commonly observed internal alkenylboron regiosomer through an α-selective borylcupration step. A variety of carbon electrophiles participate in the reaction, including allyl alcohols derivatives and alkyl halides. The method provides a straightforward and selective route to versatile tri-substituted alkenylboron compounds that are otherwise challenging to access.

A Mixture IRTree Model for Extreme Response Style: Accounting for Response Process Uncertainty.

This paper presents a mixture item response tree (IRTree) model for extreme response style. Unlike traditional applications of single IRTree models, a mixture approach provides a way of representing the mixture of respondents following different underlying response processes (between individuals), as well as the uncertainty present at the individual level (within an individual). Simulation analyses reveal the potential of the mixture approach in identifying subgroups of respondents exhibiting response behavior reflective of different underlying response processes. Application to real data from the Students Like Learning Mathematics (SLM) scale of Trends in International Mathematics and Science Study (TIMSS) 2015 demonstrates the superior comparative fit of the mixture representation, as well as the consequences of applying the mixture on the estimation of content and response style traits. We argue that methodology applied to investigate response styles should attend to the inherent uncertainty of response style influence due to the likely influence of both response styles and the content trait on the selection of extreme response categories.

A Psychometric Model for Discrete-Option Multiple-Choice Items.

Discrete-option multiple-choice (DOMC) items differ from traditional multiple-choice (MC) items in the sequential administration of response options (up to display of the correct option). DOMC can be appealing in computer-based test administrations due to its protection of item security and its potential to reduce testwiseness effects. A psychometric model for DOMC items that attends to the random positioning of key location across different administrations of the same item is proposed, a feature that has been shown to affect DOMC item difficulty. Using two empirical data sets having items administered in both DOMC and MC formats, the variability in key location effects across both items and persons is considered. The proposed model exploits the capacity of the DOMC format to isolate both (a) distinct sources of item difficulty (i.e., related to the identification of keyed responses versus the ruling out of distractor options) and (b) distinct person proficiencies related to the same two components. Practical implications in terms of the randomized process applied to schedule item key location in DOMC test administrations are considered.

Dietary effect of low fish meal aquafeed on gut microbiota in olive flounder (Paralichthys olivaceus) at different growth stages.

This study was conducted to investigate the long-term effect of a low fish meal (FM) diet comprising plant-based protein sources (PPS) on changes of gut microbial diversity in olive flounder (Paralichthys olivaceus) over the course of life. Two experimental diets were prepared to contain 74% FM (control) or 52% FM with 22% PPS (30% FM replacement, FM30). Fish were fed one of the two experimental diets for 8 months, and we collected the midgut contents to analyze the gut bacterial community by Illumina MiSeq based on the metagenomic sequences in the V3-V4 regions of 16S rRNA. We found that there were nine dominant phyla, which in turn presented Proteobacteria, Firmicutes, and Actinobacteria as the three major phyla in the gut microbiota of the flounder. At genus level, the dominant genera were Delftia, Prevotella, and Chthoniobacter at the juvenile stage (below 100 g/fish); Chthoniobacter, Bacillus, and Bradyrhizobium at the grower stage (400 g/fish); Chthoniobacter, Bacillus, and Delftia at the subadult stage (800 g/fish); and Lactobacillus and Prevotella at the adult stage (over 1,000 g/fish). The microbial diversity in olive flounders arched from the juvenile and subadult stage and reached a plateau thereafter. The fish fed the FM30 diet significantly had an increased abundance of Lactobacillus and Photobacterium and had less abundance of Prevotella and Paraprevotella than the control. However, the effect of dietary PPS was not significant on total microbial richness, indicating no negative effect as feed sources on the intestinal microbiota in olive flounder. These results indicate that the life stage of olive flounder is more important in modulating intestinal microbiota than is the diet. It could also be concluded that dietary PPS might be used as a potential fish meal alternative without any compromising effects on microbial diversity of olive flounder for long-term feeding.

Ionization of gold (γ-methoxy)vinyl complexes generates reactive gold vinyl carbene complexes.

Cationic gold vinyl carbene/allylic cation complexes of the form (E)-[(L)AuC(H)C(H)CAr2]+ OTf- {L = IPr, Ar = Ph [(E)-5a], L = IPr, Ar = 4-C6H4OMe [(E)-5b], L = P(t-Bu)2 o-biphenyl, Ar = 4-C6H4OMe [(E)-5c]} were generated in solution via Lewis acid-mediated ionization of the corresponding gold (γ-methoxy)vinyl complexes (E)-(L)AuC(H)C(H)C(OMe)Ar2 at or below -95 °C. Complexes (E)-5b and (E)-5c were fully characterized in solution employing multinuclear NMR spectroscopy, which established the predominant contribution of the aurated allylic cation resonance structure and the significant distribution of positive charge into the γ-anisyl rings. Complex (E)-5b reacted rapidly at -95 °C with neutral two-electron, hydride, and oxygen atom donors exclusively at the C1 position of the vinyl carbene moiety and with p-methoxystyrene to form the corresponding vinylcyclopropane. In the absence of nucleophile (E)-5a decomposed predominantly via intermolecular carbene dimerization whereas formation of 1-aryl-5-methoxy indene upon ionization of (Z)-(IPr)AuC(H)C(H)C(OMe)(4-C6H4OMe)2 [(Z)-6b] implicated an intramolecular Friedel-Crafts or electrocyclic Nazarov pathway for the decomposition of the unobserved vinyl carbene complex (Z)-[(IPr)AuC(H)C(H)C(4-C6H4OMe)2]+ OTf- [(Z)-5b].

Synthesis of gold allyloxysulfonium complexes and elimination to form an α,ß-unsaturated aldehyde.

Treatment of the gold vinyl carbene/allylic cation complex (E)-[(IPr)AuC(H)C(H)C(4-C6H4OMe)2]+ OTf- with sulfoxides at -95 °C formed the corresponding gold allyloxysulfonium complexes [(IPr)AuC(H)(OSR2)C(H)[double bond, length as m-dash]C(4-C6H4OMe)2]+ OTf- [R = Me, -(CH2)4-, Ar] in ≥95 ± 5% NMR yield. Allyloxysulfonium gold complexes underwent elimination at or below room temperature to form 3,3-bis(4-methoxyphenyl)acrylaldehyde in ≥67% yield.