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A straightforward method for the undirected trifluoromethylation of unactivated methylene units was developed. The reaction proceeds in aqueous acetonitrile with Grushin's reagent, bpyCu(CF3)3, under broad-spectrum white-light irradiation. The trifluoromethylation tolerates a wide range of functional groups including ketones, esters, nitriles, amides, alcohols, and carboxylic acids. The C-H cleavage step is performed via intermolecular H atom abstraction, and the selectivities across a range of methylene units are reported. Mechanistic studies offer a general reaction coordinate for the overall transformation.

GaCl3 and (IPr)GaCl3/AgSbF6 formed γ-tertiary and γ-quaternary carbons via homoconjugate addition of organoboron nucleophiles to diester- and ketone-functionalized cyclopropanes. Electron donor group cyclopropane substituents were not needed, allowing electron-deficient aryl, alkenyl, alkyl, and hydrogen-substituted cyclopropanes to be used. The catalytic conditions were compatible with alkenyl, alkynyl, and aryl nucleophiles, including ortho-substituted aromatics, to synthesize highly hindered quaternary carbons. Alkynyl nucleophiles formed substituted cyclopentenes. A control experiment supports an intermediate carbocation in quaternary carbon center formation.

This account chronicles the iterative development of an enantioselective conjugate addition of organoboron nucleophiles to α,β-unsaturated enones and enals catalyzed by BINOL derivatives. Beginning with a specific application of this transformation to the total synthesis of the flinderole alkaloids, the transformation progressed to encompass a much larger scope of heterocycle-substituted electrophiles. The next phase saw progress toward the use of a broader scope of functional nucleophiles, with application in a strategy to synthesize discoipyrrole D. At each stage of this chronologically organized discussion, key problems, hypotheses, and solutions are presented to show the sources of discovery and solutions to problems as the catalyst and other reaction components were made more reactive. The interplay of target-directed reaction development, efforts to increase the scope of compatible functional groups, mechanistic studies, and empirical exploration is described to illustrate sources of chemical discovery.1 Introduction2 Synthesis of the Flinderole Natural Products3 Indole-Bearing Stereocenters4 Heteroaryl-Bearing Stereocenters5 Bis-Heteroaryl Stereocenters6 Synthetic Strategy for Discoipyrrole D7 Bis-Aryl Stereocenters8 Remaining Challenges9 Conclusion

This review covers the use of organoboron nucleophiles in enantioselective conjugate additions catalyzed by organic-based catalysts. It is divided into sections based on the type of nucleophile, with each section arranged in roughly chronological order. The categories of nucleophiles are alkynyl, alkenyl, and aryl boronates or borates. The principle modes of catalysis, iminium formation and boron chelation, are covered.

A novel and practical homoconjugate addition of alkenyl, alkynyl, heteroaryl, and aryl trifluoroborates to arylated cyclopropyl ketones to synthesize γ,γ-disubstituted ketones is reported. A preliminary mechanistic proposal involving ketone protonation, an intermediary carbocation, and intermolecular nucleophile addition has been made based on control studies.

Herein, we report the synthesis, structural characterization, and catalytic properties of a new cobalt-based metal–organic framework, Co2(BDC)2(DABCO) (where BDC = 1,4-benzenedicarboxylate and DABCO = 1,4-diazabicyclo[2.2.2]octane), namely VNU-10 (where VNU = Vietnam National University). Single-crystal X-ray diffraction analysis revealed that VNU-10 crystallizes in the hexagonal space group P6/mmm. The structure of this material is comprised of two-dimensional kgm layers which are interconnected by DABCO pillars to afford an overall three-dimensional porous architecture. VNU-10 exhibited exceptional catalytic activity toward the direct amination of oxazoles via C–H/N–H couplings while a previously reported topological isomer, Co2(BDC)2(DABCO), with the sql topology, displayed poor activity. Leaching tests indicated that homogeneous catalysis via leached active cobalt species is unlikely. Furthermore, the VNU-10 catalyst was facilely isolated from the reaction mixture and reused several times without degradation of the catalytic reactivity.

A practical catalytic method to synthesize β,β- and γ,γ-substituted amines by opening aziridines and azetidines, respectively, using alkenyl, alkynyl, or aryl/heteroaryl trifluoroborate salts is described. This reaction features simple open-flask reaction conditions, the use of transition-metal-free catalysis, complete regioselectivity, and high diastereoselectivity. Preliminary mechanistic studies suggest that carbocation formation is disfavored. Stereoretentive addition is favored with Bronsted acid present, while stereoinversion is favored in its absence, indicating divergent mechanisms.

Organocatalysis has emerged as a powerful synthetic tool in organic chemistry in the last few decades. Among various classes of organocatalysis, chiral diol-based scaffolds, such as BINOLs, VANOLs, and tartaric acid derivatives, have been widely used to induce enantioselectivity due to the ability of the hydroxyls to coordinate with the Lewis acidic sites of reagents or substrates and create a chiral environment for the transformation. In this review, we will discuss the applications of these diol-based catalysts in different types of reactions, including the scopes of reactions and the modes of catalyst activation. In general, the axially chiral aryl diol BINOL and VANOL derivatives serve as the most competent catalyst for most examples, but examples of exclusive success using other scaffolds, herein, suggests that they should not be overlooked. Lastly, the examples, to date, are mainly from tartrate and biaryl diol catalysts, suggesting that innovation may be available from new diol scaffolds.

We analyse cosmological hydrodynamical simulations of galaxy clusters to study the X-ray scaling relations between total masses and observable quantities such as X-ray luminosity, gas mass, X-ray temperature, and $Y_{X}$. Three sets of simulations are performed with an improved version of the smoothed particle hydrodynamics GADGET-3 code. These consider the following: non-radiative gas, star formation and stellar feedback, and the addition of feedback by active galactic nuclei (AGN). We select clusters with $M_{500} > 10^{14} M_{\odot} E(z)^{-1}$, mimicking the typical selection of Sunyaev-Zeldovich samples. This permits to have a mass range large enough to enable robust fitting of the relations even at $z \sim 2$. The results of the analysis show a general agreement with observations. The values of the slope of the mass-gas mass and mass-temperature relations at $z=2$ are 10 per cent lower with respect to $z=0$ due to the applied mass selection, in the former case, and to the effect of early merger in the latter. We investigate the impact of the slope variation on the study of the evolution of the normalization. We conclude that cosmological studies through scaling relations should be limited to the redshift range $z=0-1$, where we find that the slope, the scatter, and the covariance matrix of the relations are stable. The scaling between mass and $Y_X$ is confirmed to be the most robust relation, being almost independent of the gas physics. At higher redshifts, the scaling relations are sensitive to the inclusion of AGNs which influences low-mass systems. The detailed study of these objects will be crucial to evaluate the AGN effect on the ICM., 24 pages, 11 figures, 5 tables, replaced to match accepted version

Recent X-ray observations of galaxy clusters show that the distribution of intra-cluster medium (ICM) metallicity is remarkably uniform in space and time. In this paper, we analyse a large sample of simulated objects, from poor groups to rich clusters, to study the dependence of the metallicity and related quantities on the mass of the systems. The simulations are performed with an improved version of the Smoothed-Particle-Hydrodynamics \texttt{GADGET-3} code and consider various astrophysical processes including radiative cooling, metal enrichment and feedback from stars and active galactic nuclei (AGN). The scaling between the metallicity and the temperature obtained in the simulations agrees well in trend and evolution with the observational results obtained from two data samples characterised by a wide range of masses and a large redshift coverage. We find that the iron abundance in the cluster core ($r, MNRAS, accepted

We analyze the radial pressure profiles, the ICM clumping factor and the Sunyaev-Zel'dovich (SZ) scaling relations of a sample of simulated galaxy clusters and groups identified in a set of hydrodynamical simulations based on an updated version of the TreePM-SPH GADGET-3 code. Three different sets of simulations are performed: the first assumes non-radiative physics, the others include, among other processes, AGN and/or stellar feedback. Our results are analyzed as a function of redshift, ICM physics, cluster mass and cluster cool-coreness or dynamical state. In general, the mean pressure profiles obtained for our sample of groups and clusters show a good agreement with X-ray and SZ observations. Simulated cool-core (CC) and non-cool-core (NCC) clusters also show a good match with real data. We obtain in all cases a small (if any) redshift evolution of the pressure profiles of massive clusters, at least back to z=1. We find that the clumpiness of gas density and pressure increases with the distance from the cluster center and with the dynamical activity. The inclusion of AGN feedback in our simulations generates values for the gas clumping ($\sqrt C_{\rho}\sim 1.2$ at $R_{200}$) in good agreement with recent observational estimates. The simulated $Y_{SZ}-M$ scaling relations are in good accordance with several observed samples, especially for massive clusters. As for the scatter of these relations, we obtain a clear dependence on the cluster dynamical state, whereas this distinction is not so evident when looking at the subsamples of CC and NCC clusters., Comment: 22 pages, 14 figures, 2 tables. Submitted to MNRAS