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Acetylene and aldehydes are coupled through cyclometallation and silane-mediated σ-bond metathesis to synthesize various vinyl-substituted alcohols. This reaction features good functional group tolerance using acetylene as a C2 synthon.

A highly efficient redox- and step-economic method to synthesize N,O- and O,O-difluoroboron complexes from alkynes under aqueous condition with HBF4 as BF2 source has been developed. This strategy features good yields, broad substrate scope, mild reaction conditions, readily available starting materials and gram-scale synthesis. Significantly, these difluoroboron complexes present good fluorescence properties, indicating their potential applications in luminescent materials.

The highly efficient homo-dimerization and cross-coupling of propargyl esters via migratory insertion of the copper-allenylidenes have been developed to give various 1-en-3,5-diynes, [5]cumulenes and 1,3-diynes with moderate to excellent yields.

The chiral dirhodium(ii) tetracarboxylate-catalyzed enantioselective intramolecular Büchner reaction and aromatic substitution of donor/donor-carbenes were reported and a series of valuable chiral polycyclic products were synthesized.

The first palladium-catalyzed intramolecular enantioselective C(sp3)–H insertion of donor–donor carbenes has been achieved. The diazo compounds afford rare trans-indolines with excellent enantioselectivities, while enynones deliver cis-indolines exclusively.

An efficient semi-pinacol rearrangement strategy of enynals involving a metal carbene intermediate has been developed, which allows the practical synthesis of various functionalized α-furanyl ketones in moderate to good yields under mild reaction conditions.

Dirhodium-catalyzed transformations, not limited to carbene and nitrene transfer reactions, are reviewed, including cycloisomerization, hetero-Diels–Alder (HDA) reactions, ene reactions, arylation, radical oxidation reactions and C–H activation, etc.

Tuning the photophysical properties of π-conjugated oligomers by functionalization of skeleton, to achieve an optically and electronically advantageous building block for organic semiconductor materials is a vital yet challenging task. In this work, a series of structurally well-defined polyaryl-functionalized α-oligofurans, in which aryl groups are introduced precisely into each of the furan units, are rapidly and efficiently synthesized by de novo synthesis of α-bi(arylfuran) monomers for the first time. This new synthetic strategy nicely circumvents the cumbersome substituent introduction process in the later stage by preinstall of the desired aryl groups in the starting material. The characterization of α-oligo(arylfuran)s demonstrates that photoelectric properties of coplanar α-oligo(arylfuran)s can be tuned through varying aryl groups with different electrical properties. These novel α-oligo(arylfuran)s have good hole transport capacity and can function as hole-transporting layers in organic light-emitting diodes, indicative of significant breakthrough in the application of α-oligofurans materials in OLEDs. And our findings offer an avenue for the ingenious use of α-oligo(arylfuran)s as p-type organic semiconductors for OLEDs.

The vinyl-gold bond is easily accessible but less exploited in homogeneous gold catalysis, which possesses weak nucleophilicity and would be likely to undergo protodemetalation. Herein, a gold-catalyzed enynal and enynol coupling by selectively steering two transient vinyl-gold intermediates is realized under mild conditions. It exhibits high atom economy and good tolerance of functional groups with the added benefit of operational simplicity. The control experiments indicated that the in situ formed vinyl-gold accounts for the reactivity.

Hydrogen atom transfer (HAT) process is a powerful and effective strategy for activating C-H bonds followed by further functionalization. Intramolecular 1,n (n = 5 or 6)-HATs are common and frequently encountered in organic synthesis. However, intramolecular 1,n (n = 2 or 3)-HAT is very challenging due to slow kinetics. Compared to proton-shuttle process, which is well established for organic synthesis, hydrogen radical-shuttle (HRS) is unexplored. In this work, a HRS-enabled decarboxylative annulation of carbonyl compounds via photoredox catalysis for the synthesis of indanones is developed. This protocol features broad substrate scope, excellent functional group tolerance, internal hydrogen radical transfer, atom- and step-economy. Critical to the success of this process is the introduction of water, acting as both HRS and hydrogen source, which was demonstrated by mechanistic experiments and density functional theory (DFT) calculations. Importantly, this mechanistically distinctive HAT provides a complement to that of typical proton-shuttle-promoted, representing a breakthrough in hydrogen radical transfer, especially in the inherently challenging 1,2- or 1,3-HAT., Although hydrogen atom transfer is widely observed in synthetic organic chemistry, intramolecular hydrogen atom transfer between atoms separated by fewer than four bonds is kinetically slow. Here the authors show a method to form indanones, with hydrogen atoms shuttled across short distances by water.

Described herein is an enantioselective dirhodium(II)-catalyzed cycloisomerization of diynes achieved by the strategy of desymmetrization, which not only represents a new cycloisomerization reaction of diynes but also constitutes the first Rh(II)-catalyzed asymmetric intramolecular cycloisomerization of 1,6-diynes. This protocol provides a range of valuable furan-fused dihydropiperidine derivatives with an enantiomerically enriched alkynyl-substituted aza-quaternary stereocenter in high efficiency, complete atom economy, and excellent enantioselectivity (up to 98% ee). Besides, the highly functionalized products could be easily transformed into various synthetically useful building blocks and conjugated with a series of pharmaceutical molecules. The mechanism involving a concerted [3+2] cycloaddition/[1,2]-H shift of the Rh(II) carbenoid intermediate was elucidated by DFT calculations and mechanistic studies. More importantly, the first single crystal of alkyne-dirhodium(II) was obtained to show that a η2-coordinating activation of alkynal by dirhodium(II) was involved. Weak hydrogen bondings between the carboxylate ligands and alkynal were found, which probably made the well-defined paddlewheel-like dirhodium(II) distinctive from other metal complexes in catalyzing this transformation. Furthermore, the origin of the enantioselectivity was elucidated by a Rh2(R-PTAD)4-alkyne complex and additional calculational studies.

Heterophanes are widely found in natural products and drug molecules. Herein, an efficient method for the construction of [2,5]-furanophanes with different ring types and ring sizes was developed. This method is carried out with furan-free precursor through intramolecular carbene-mediated alkynyl migration and tandem cyclization strategy. In addition, a series of tetrafuran structures can be obtained by oxidative coupling of the products.

Prostate cancer (PCa) is the most frequently diagnosed male malignant tumor and remains the second leading cause of male cancer mortality in western countries. The development of novel antiandrogens to circumvent the drug resistance in anti-PCa treatment is highly demanded. Herein, we identified that gossypol (GOS) specificly inhibited the AR signaling. Further optimization of GOS derivatives led to the discovery of compound XY-32. XY-32 efficiently inhibits AR signaling with the IC

A series of highly strained bicyclo[3.n.1]alkenones have been successfully constructed in good-to-excellent enantioselectivities and moderate-to-good yields via copper-catalyzed formal [3+3] cycloa...

The study of sedimentary characteristics and genetic mechanism of mixed siliciclastic-carbonate sediments (MSCSs) is not only the focus of sedimentary geology, but it is also an important issue in petroleum exploration and development. We have discovered the lacustrine MSCSs, the interstratified siliciclastic-carbonate sediments and the textural mixture of siliciclastic and carbonate materials (s-MSCSs) in the second member of the Paleogene Funing Formation ([Formula: see text]) in the Gaoyou and Jinhu sags, Subei Basin, eastern China. We use core, mud-log and thin-section data to clarify the [Formula: see text] s-MSCSs into five types, and we also use geochemical data of the [Formula: see text] mudstone including X-ray diffraction (XRD) whole rock, XRD clay, and trace elements to quantitatively analyze lake paleosalinity. The [Formula: see text] s-MSCSs mainly consist of siliciclasts, ooids, intraclasts, and mud, and they could be siliciclast-dominated, allochem-dominated, or without dominant components. We analyze that mixed sediments occur under either traction flow or gravity flow. The s-MSCSs of the traction flow origin develop small-scale, wavy cross-bedding and consist of siliciclasts and ooids of similar size; the s-MSCSs of the gravity flow origin develop massive bedding and graded bedding with complex lithology, and they mainly consist of siliciclasts and allochems of different size. We hypothesize that the increase of lake paleosalinity controlled by the climate and the moderate siliciclast influx under stable tectonic setting provide the material source for s-MSCSs in the lacustrine basin. Multidirectional flow is common during the deposition of s-MSCSs of traction flow origin, and seasonal flooding produces s-MSCSs of the gravity flow origin. Lacustrine s-MSCSs in the Gaoyou and Jinhu sags have significantly smaller scale and quantity, and ooids rather than bioclasts occupy most of the carbonate components.

Described herein is a dirhodium(ii)-catalyzed asymmetric cycloisomerization reaction of azaenyne through a cap-tether synergistic modulation strategy, which represents the first catalytic asymmetric cycloisomerization of azaenyne. This reaction is highly challenging because of its inherent strong background reaction leading to racemate formation and the high capability of coordination of the nitrogen atom resulting in catalyst deactivation. Varieties of centrally chiral isoindazole derivatives could be prepared in up to 99 : 1 d.r., 99 : 1 er and 99% yield and diverse enantiomerically enriched atropisomers bearing two five-membered heteroaryls have been accessed by using an oxidative central-to-axial chirality transfer strategy. The tethered nitrogen atom incorporated into the starting materials enabled easy late-modifications of the centrally and axially chiral products via C–H functionalizations, which further demonstrated the appealing synthetic utilities of this powerful asymmetric cyclization., Rh(ii)-catalyzed asymmetric cycloisomerization of azaenyne through a cap-tether synergistic modulation strategy was described. Diverse centrally and axially chiral isoindazoles were prepared and directed C–H late-stage modifications were developed.

The construction of partially protected nonsymmetrical biaryldiols catalyzed by AgBF4 has been achieved. The approach facilitates the formation of two new aryl rings and the introduction of two hydroxyl groups (one free and one TBS-protected) via the o-NQM generation/semipinacol rearrangement cascade, featuring high atom- and step-economy to afford a diverse array of partially protected nonsymmetrical biaryldiols under mild conditions.

The Sulige gas field in the Ordos Basin is the largest gas field in China. The studied area, the northern Tianhuan depression, is located west of the gas field and is considered as a potential gas-producing area. The complex diagenetic alteration history and its effects on the pore-throat network and reservoir quality of the tight gas sandstones are explained. The upper Paleozoic first member of the Shanxi Formation and eighth member of the Shihezi Formation tight gas reservoir rocks are composed of coarse- to medium-grained sandstones and are dominated by sublitharenites. The most important diagenetic factor for porosity reduction was compaction, followed by cementation. Diagenetic mineral phases include quartz overgrowth, calcite cement and replacement, and kaolinite cement and replacement, with minor heulandite and chlorite. Pressure dissolution of quartz grains and quartzite fragments is the main source of silica for the early and late quartz overgrowth cementation (formed mainly from 120°C to 140°C). The hydrolysis and alteration of volcanic material and mica flakes released some silicon, calcium, and aluminum ions. Calcium and carbon in calcite cements could be derived from surrounding mudstones. Calcite replaced the quartz overgrowths. The formation of kaolinite, as cement and replacements, was controlled by the interactions of silica, aluminum, pH, and temperature (140°C). Because of deformation of detrital components (mica flakes and ductile rock fragments) and diagenetic replacement, clear negative correlations between reservoir quality and contents of the diagenetic minerals are lacking. A complex and isolated pore-throat network was created by strong diagenetic transformation. Based on analysis of thin sections, three-dimensional x-ray micro–computed tomography, and constant-rate mercury injection data, the samples with relatively good reservoir quality (porosity >10% and permeability >0.5 md) are characterized by dissolution pores and primary intergranular pores and commonly contain more and larger pore throats both in volume (counts >1800 and size >0.02 per unit volume) and diameter (>1.20 μm) than the samples with poor reservoir quality. The intercrystalline pores of kaolinite are very widespread and considered favorable for oil and gas accumulation because some asphalt was found within these pores. This study may be used, by analogy, to better understand diagenetic factors controlling the formation of tight gas sandstone reservoirs and predict the development of pore-throat systems.

A copper-catalyzed three-component carboboration of acetylene with B2Pin2 and Michael acceptors was achieved. The small acetylene molecule enabled faster rate of borylcupration and easier C–C bond formation compared with substituted alkynes.

We report the first Rh2(II)-catalyzed asymmetric cycloisomerization of activated enynes to provide cyclopropane-fused tetrahydropyridines in good yields and excellent enantioselectivities under mild conditions. The activated group, CHZ (Z is electron-withdrawing group (EWG)), in the enyne substrates exerts two synergetic roles, one is to activate alkyne for the cyclopropanation reaction; the other is to introduce the C–H···O interaction between substrate and catalyst (reducing the energy barrier of the reaction). This double-mode activation was supported by both density functional theory (DFT) calculations and experimental tests. This strategy was also extended to other CH2Z (Z can be OH, OMe, F) as activating groups that made the CH2 more acidic so that the substrates could also form increased C–H···O interaction with the catalyst.

An unprecedented deconstructive reorganization strategy for the de novo synthesis of hydroxylated benzofurans from kojic acid- or maltol-derived alkynes is reported. In this reaction, both the benzene and furan rings were simultaneously constructed, whereas the pyrone moiety of the kojic acid or maltol was deconstructed and then reorganized into the benzene ring as a six-carbon component. Through this strategy, at least one free hydroxyl group was introduced into the benzene ring in a substitution-pattern tunable fashion without protection-deprotection and redox adjustment. With this method, a large number of hydroxylated benzofuran derivatives with different substitution-patterns have been prepared efficiently. This methodology has also been shown as the key step in a collective total synthesis of hydroxylated benzofuran-containing natural products (11 examples).

The 1,4-addition reaction of ortho-naphthoquinone methide (o-NQM) intermediates induced by silver-catalyzed ring formation with electron-rich aromatic compounds and α-methylene ketones has been developed. This reaction provides an efficient method to construct versatile unsymmetrical triarylmethanes and benzo[f]chromenes under mild conditions. This transient intermediate was inseparable due to reversible dimerization but could be stored by forming a boric acid adduct for further transformations.

Correction for ‘Synthesis of vinyl-substituted alcohols using acetylene as a C2 building block’ by Zhicong Lin et al., Chem. Sci., 2023, https://doi.org/10.1039/d2sc06400f.

A novel type of burial dolomitization related to alteration of intermediate volcaniclastic rocks is discussed based on mineralogical, petrological and geochemical analyses. Lacustrine, fine-grained (