Click assembly through selective azaylide formation.

An efficient triple-click assembly using a newly designed trivalent platform is disclosed. We achieved the selective azaylide formation of 2,3,5,6-tetrafluorophenyl azides with o-ester-substituted triarylphosphines leaving 2,6-dichlorophenyl azides untouched. Further rapid Staudinger reaction of dichlorophenyl azides and subsequent triazole formation allowed us to prepare trifunctionalized molecules in three steps.

Iterative click reactions using trivalent platforms for sequential molecular assembly.

A facile synthesis of multi(triazole)s by iterative click reactions is disclosed. Good functional group tolerance of sequential click assembly by sulfur-fluoride exchange (SuFEx), copper-catalyzed azide-alkyne cycloaddition (CuAAC), and thia-Michael reaction realizes the iterative click reactions. Diverse multi(triazole)-type mid-molecules can be synthesized easily from readily available modules through good chemoselective reactions without functional group transformation steps.

Bromothiolation of Arynes for the Synthesis of 2-Bromobenzenethiol Equivalents.

A new method to synthesize o-bromobenzenethiol equivalents through aryne intermediates is disclosed. Various o-bromobenzenethiol equivalents are prepared by the bromothiolation of aryne intermediates with potassium xanthates. Aryl xanthates serve in the synthesis of diverse organosulfurs involving phenothiazines and thianthrenes by further transformations.

Highly substituted benzo[b]furan synthesis through substituent migration.

An unusual benzofuran synthesis from 2,6-disubstituted phenols and alkynyl sulfoxides is disclosed. Various highly substituted benzofurans were synthesized via the charge-accelerated [3,3]-sigmatropic rearrangement and subsequent substituent migration. Multiaryl-substituted benzofurans and fully substituted benzofurans were prepared on the basis of the unique reaction mechanism.

High-entropy engineering of the crystal and electronic structures in a Dirac material.

Dirac and Weyl semimetals are a central topic of contemporary condensed matter physics, and the discovery of new compounds with Dirac/Weyl electronic states is crucial to the advancement of topological materials and quantum technologies. Here we show a widely applicable strategy that uses high configuration entropy to engineer relativistic electronic states. We take the AMnSb2 (A = Ba, Sr, Ca, Eu, and Yb) Dirac material family as an example and demonstrate that mixing of Ba, Sr, Ca, Eu and Yb at the A site generates the compound (Ba0.38Sr0.14Ca0.16Eu0.16Yb0.16)MnSb2 (denoted as A5MnSb2), giving access to a polar structure with a space group that is not present in any of the parent compounds. A5MnSb2 is an entropy-stabilized phase that preserves its linear band dispersion despite considerable lattice disorder. Although both A5MnSb2 and AMnSb2 have quasi-two-dimensional crystal structures, the two-dimensional Dirac states in the pristine AMnSb2 evolve into a highly anisotropic quasi-three-dimensional Dirac state triggered by local structure distortions in the high-entropy phase, which is revealed by Shubnikov-de Haas oscillations measurements.

Facile synthesis of dibenzothiophene S-oxides from sulfinate esters.

An efficient method to prepare dibenzothiophene S-oxides is disclosed. Suzuki-Miyaura cross-coupling of 2-bromoaryl sulfinate esters with arylboronic acids selectively at the bromo group followed by electrophilic cyclization of the resulting sulfinate ester moiety provides diverse dibenzothiophene S-oxides. Further transformations including Pummerer-type C-H propargylation and aryne reactions realize to synthesize highly functionalized dibenzothiophene derivatives.

Synthesis of 1,2,3-triazoles using Grignard reactions through the protection of azides.

An efficient method to prepare organomagnesium intermediates having a protected azido group is reported. Protection of azido groups with di-(tert-butyl)(4-(dimethylamino)phenylphosphine (amphos) and following iodine-magnesium exchange realized the preparation of organomagnesium intermediates, which served in the synthesis of diverse azides by transformation with various electrophiles followed by deprotection with elemental sulfur. Furthermore, click reactions of azides with alkynes enabled synthesizing a wide variety of 1,2,3-triazoles.

Facile synthesis of sulfinate esters from aryl iodides via direct oxidation of thioesters.

A practical method to synthesize sulfinate esters from aryl iodides is disclosed. Direct oxidation of thioesters prepared by copper-catalyzed C-S formation of aryl iodides realized the efficient synthesis of sulfinate esters. Due to the good accessibility of aryl iodides, a wide variety of sulfinate esters were prepared from easily available starting materials such as carboxylic acids and anilines.

Chemical Aspect of Displacive-Type Ferroaxial Phase Transition from Perspective of Second-Order Jahn-Teller Effect: NASICON Systems as an Example.

Ferroaxial order, characterized by a rotational arrangement of electric dipoles, attracts increasing attention in terms of a new family of ferroic orders. However, there has been no chemical guideline for exploring crystalline materials showing ferroaxial order, namely ferroaxial materials. Here, we present a chemical guideline grounded in staggered polyhedral connectivity, which we propose as a structural prerequisite for ferroaxial order, and the second-order Jahn-Teller (SOJT) theory extended from molecular orbitals to electronic band structures. Na-superionic conductors (NASICON) including NaM2(PO4)3 (M = early-transition or post-transition metal) are identified as potential ferroaxial materials because of their staggered structures composed of MO6 octahedra and PO4 tetrahedra. However, ferroaxial phase transitions hardly occur in some of the NASICON systems, which offers a platform to uncover a hidden factor playing an important role in driving this system into ferroaxial states. Our first-principles calculations demonstrate that a ferroaxial phase transition in NASICON systems occurs only when SOJT interaction is symmetrically allowed, that is, energy-lowering chemical bonds are formed as a consequence of the distortion. Our proposals would be not limited to NASICON systems but applicable to a variety of compounds and provide new insight into the exploration of displacive-type ferroaxial materials.

C-F Transformations of Benzotrifluorides by the Activation of Ortho-Hydrosilyl Group.

Single C-F transformations of aromatic trifluoromethyl compounds are challenging issues due to the strong C-F bond. We have recently developed selective methods for single C-F transformations such as allylation of o-hydrosilyl-substituted benzotrifluorides through the hydride abstraction with trityl cations. Single C-F thiolation and azidation of o-(hydrosilyl)benzotrifluorides were achieved using trityl sulfides and trityl azide catalyzed by Yb(OTf)3 . Treatment of o-(hydrosilyl)benzotrifluorides with trityl chloride resulted in single C-F chlorination. The resulting fluorosilyl group served in further transformations including protonation, halogenation, and Hiyama cross-coupling with C-Si cleavage. We also synthesized benzyl fluorides by LiAlH4 -reduction of the resulting fluorosilanes and further C-F transformations. These methods enabled us to prepare a broad range of organofluorines from simple benzotrifluorides through C-F and C-Si transformations.

Synthesis of benzo[b]furans from alkynyl sulfoxides and phenols by the interrupted Pummerer reaction.

The interrupted Pummerer reaction of alkynyl sulfoxides with phenols is disclosed. A wide range of benzo[b]furans were efficiently synthesized through unexplored electrophilic activation of the electron-deficient alkynyl sulfinyl group. Based on the good availability of alkynyl sulfoxides, we successfully prepared various functionalized benzo[b]furans from readily available alkynes, thiosulfonates, and phenols.

Topochemical Synthesis of LiCoF3 with a High-Temperature LiNbO3-Type Structure.

A novel perovskite fluoride, LixCoF3, which has an exceptionally low tolerance factor (0.81), has been synthesized via low-temperature lithium intercalation into a distorted ReO3-type fluoride CoF3 using organolithium reagents. Interestingly, this reaction is completed within 15 min at room temperature. Synchrotron X-ray diffractometry and optical second harmonic generation at room temperature have revealed that this compound shows a high-temperature LiNbO3-type structure (space group: R3̅c) involving Li-Co antisite defects and A-site splitting along the c direction. A-site splitting is consistent with the prediction based on hybrid Hartree-Fock density functional theory calculations. Co-L2,3 edge X-ray absorption spectroscopy, as well as bond valence sum analysis, has verified the divalent oxidation state of Co ions in the lithiated phase, suggesting that its composition is close to LiCoF3 (x ≈ 1). This compound exhibits a paramagnetic-to-antiferromagnetic transition at 36 K on cooling, accompanied by weak ferromagnetic ordering. The synthetic route based on low-temperature lithiation of metal fluorides host paves the way for obtaining a new LiNbO3-type fluoride family.

Azido-type-selective triazole formation by iridium-catalyzed cycloaddition with thioalkynes.

The iridium-catalyzed azide-thioalkyne cycloaddition was found to proceed much faster with benzyl azide than with phenyl azide. The high azido-type selectivity was also observed in other combinations of azides with different steric environments. This finding enabled the efficient assembly of three azidophilic molecules to triazido platforms by three sequential triazole-forming reactions.

Hydride reduction of o-(fluorosilyl)benzodifluorides for subsequent C-F transformations.

An efficient method for sequential C-F transformations of o-hydrosilyl-substituted benzotrifluorides is disclosed. A key to the success is hydride reduction of o-fluorosilyl-substituted difluoromethylenes prepared by a single C-F transformation of o-hydrosilyl-substituted benzotrifluorides. We succeeded in further C-F transformations via hydride abstraction of the resulting o-hydrosilyl group, enabling us to synthesize a wide variety of organofluorine compounds.

Modular synthesis of triazoles from 2-azidoacrylamides having a nucleophilic amino group.

Assembling methods using 2-azidoacrylamides having a nucleophilic amino group are disclosed. Divergent transformations of the amine-type trivalent platform were accomplished with a wide variety of electrophiles to obtain a broad range of 2-azidoacrylamides involving a fluorosulfonyl group-containing trivalent platform. Consecutive click conjugations including triazole formation, thiol-ene-type 1,4-addition, and SuFEx reactions realized the efficient assembly of easily available simple modules.

Electronic Origin of Non-Zone-Center Phonon Condensation: Octahedral Rotation as a Case Study.

Unstable zone-boundary phonon modes drive atomic displacements linked to a rich array of properties. Yet, the electronic origin of the instability remains to be clearly explained. In this Letter, we propose that bonding interaction between Bloch states belonging to different wave vectors leads to such instability via the pseudo- or second-order Jahn-Teller effect. Our first-principles calculations and representation theory-based analyses show that rotations of anion coordinated octahedra, an archetypal example of zone-boundary phonon condensations, are induced by this bonding mechanism. The proposed mechanism is universal to any non-zone-center phonon condensations and could offer a general approach to understanding the origin of structural phase transitions in crystals.

Synthesis of Azidoanilines by the Buchwald-Hartwig Amination.

We report a Buchwald-Hartwig amination compatible with azido functionality. Treatment of azidoaryl iodides and amines with fourth-generation Buchwald precatalyst coordinated by CPhos and sodium tert-butoxide in 1,4-dioxane at 50 °C afforded the corresponding azidoanilines while leaving the azido groups intact. The method showed a broad substrate scope and was applicable to the synthesis of diazido compounds as photoaffinity probe candidates of pharmaceutical amines and multiazido platform molecules.

Nucleophilic transformations of azido-containing carbonyl compounds via protection of the azido group.

Nucleophilic transformations of azido-containing carbonyl compounds are discussed. The phosphazide formation from azides and di(tert-butyl)(4-(dimethylamino)phenyl)phosphine (Amphos) enabled transformations of carbonyl groups with nucleophiles such as lithium aluminum hydride and organometallic reagents. The good stability of the phosphazide moiety allowed us to perform consecutive transformations of a diazide through triazole formation and the Grignard reaction.

Diamond formation from methane hydrate under the internal conditions of giant icy planets.

Hydrocarbon chemistry in the C-O-H system at high pressure and high temperature is important for modelling the internal structure and evolution of giant icy planets, such as Uranus and Neptune, as their interiors are thought to be mainly composed of water and methane. In particular, the formation of diamond from the simplest hydrocarbon, i.e., methane, under the internal conditions of these planets has been discussed for nearly 40 years. Here, we demonstrate the formation of diamond from methane hydrate up to 3800 K and 45 GPa using a CO2 laser-heated diamond anvil cell combined with synchrotron X-ray diffraction, Raman spectroscopy, and scanning electron microscopy observations. The results show that the process of dissociation and polymerisation of methane molecules to produce heavier hydrocarbons while releasing hydrogen to ultimately form diamond proceeds at milder temperatures (~ 1600 K) and pressures (13-45 GPa) in the C-O-H system than in the C-H system due to the influence of water. Our findings suggest that diamond formation can also occur in the upper parts of the icy mantles of giant icy planets.

Palladium-Catalyzed Sulfinylation of Aryl- and Alkenylborons with Sulfinate Esters.

An efficient, direct sulfinylation of organoborons catalyzed by palladium is disclosed. Treatment of organoborons and sulfinate esters in the presence of a palladium precatalyst provided a broad range of sulfoxides. Various organosulfur compounds having oxidizable functional groups were successfully prepared through the sulfoxide synthesis.