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Myanmar is situated in Southeast Asia, where species richness and diversity are very high. Myanmar orchid flora is very rich, but still poorly known because botanical explorations have sharply decreased in Myanmar since 1950. The present study provides a checklist of Myanmar orchid flora which includes 1040 species and 151 genera currently known from Myanmar, based on the herbarium specimens, literature and online databases. The number of species is increased by approximately 200 species more than that given in the checklist of Kress et al. (2003), mainly due to recent discoveries of new species to science and new records for Myanmar. There are 76 endemic species of Orchidaceae in Myanmar. It is estimated that ca. 150–300 species still remain as unidentified and are expected to be discovered in further studies on Myanmar orchid flora.

Odontochilus putaoensis, a new species of Orchidaceae, is described and illustrated from Putao Township, Kachin State, Myanmar. Odontochilus putaoensis is close to O. duplex, but can be easily distinguished from the latter by having a light yellow lip, a bisaccate hypochile with a small, erect, blade-like and emarginate callus within each sac, a mesochile with a pair of dentate-pectinate flanges and a bilobed epichile with a pair of widely diverging lobes that are erect and concave. An identification key to the Southeast Asian species of Odontochilus and colour photographs of O. putaoensis are provided. A preliminary conservation assessment according to the IUCN Red List Categories and Criteria is given for the new species.

Gastrodia kachinensis, a new species of Orchidaceae, is described and illustrated from Putao, Kachin State, Myanmar. It is morphologically similar to G. gracilis, presumably its nearest relative, but can be easily distinguished from the latter by having perianth tube with punctate outer surface, verrucose outer surface of sepal lobe, orbicular petals, ovate-elliptic lip with truncate apex and auriculate-clawed base, glabrous lip apex with a pair of twin protuberance-like lamellae and column with a pair of blade-like lateral wings and acute stelidia at apex. Identification key and colour photographs are provided. A preliminary risk-of-extinction assessment, according to the IUCN Red List Categories and Criteria, is given for the new species.

Coelogyne putaoensis, a new species of section Ocellatae from Putao, Kachin State, Myanmar, is described and illustrated. It is morphologically similar to C. taronensis and C. weixiensis, presumably its nearest relatives. An identification key and colour photographs are provided. A preliminary risk-of-extinction assessment according to the IUCN Red List categories and criteria is given for the new species.

Axially chiral tetrasubstituted alkenes are of increasing value and interest in chemistry-related areas. However, their catalytic asymmetric synthesis remains elusive, due to the high steric repulsion and relatively low conformational stability. Herein, we disclose the straightforward construction of atropisomeric tetrasubstituted alkenes via an effective enantiocontrol of vinyl cations. This copper-catalyzed enantioselective C(sp2)-H functionalization of sterically hindered (hetero)arenes with vinyl cations enables the efficient and atom-economical preparation of axially chiral acyclic tetrasubstituted styrenes and pyrrolyl ethylenes with high atroposelectivities. Importantly, this reaction represents the first example for the assembly of axially chiral alkenes through vinyl cation approach. Computational mechanistic studies reveal the reaction mechanism, origin of regioselectivity, Z/E selectivity and enantioselectivity. The synthetic utility has been demonstrated by diverse product derivatizations, chiral organocatalyst synthesis, as well as further applications in asymmetric catalysis., (© 2024 Wiley‐VCH GmbH.)

The asymmetric Büchner reaction and related arene cyclopropanations represent one type of the powerful methods for enantioselective dearomatization. However, examples of asymmetric Büchner reactions via a non-diazo approach are quite scarce, and the related arene cyclopropanation based on alkynes has not been reported. Herein, we disclose an asymmetric Büchner reaction and the related arene cyclopropanation by copper-catalyzed controllable cyclization of N-propargyl ynamides via vinyl cation intermediates, leading to chiral tricycle-fused cycloheptatrienes and benzonorcaradienes in high yields and enantioselectivities. Importantly, this protocol represents an asymmetric arene cyclopropanation reaction of alkynes and an asymmetric Büchner reaction based on vinyl cations., (© 2024. The Author(s).)

Actinides with 5f6d7s valence orbitals feature special physicochemical properties different from those of the other elements. Actinide-based two-dimensional (2D) materials combine the distinctive physics of actinides with the quantum size effect of 2D materials, but relevant studies are scarce. Since Th has a valence electron configuration of 6d 2 7s 2 like Ti, and Ti-based MXenes show excellent stability and versatile applications, whether Th can form stable MXenes has become an intriguing question. Herein, we designed Th 2 N, Th 3 N 2 , and Th 4 N 3 MXenes and investigated their physical properties, functionalization, and potential applications using density functional theory. Their stabilities are validated by global minimum search, phonon spectra, ab initio molecular dynamics, enthalpy of formation, and energy above the hull. All the Th-N MXenes exhibit metallic properties and are stabilized by the electrostatic interaction between Th and N ions, as well as the covalent bonding interaction between the Th 6d/5f and N 2p/2s orbitals. The H-, O-, and F-functionalization 3 N 2 MXene improve its stability while preserving its metallicity, and the O-functionalized Th 3 N 2 MXene shows promising catalytic activity for hydrogen evolution. The thorium nitride MXenes enrich the family of actinide-based 2D materials and extend our understanding of the structures and properties induced by actinide elements in low-dimensional materials.

One-carbon ring expansion reaction of N-heterocycles has gained particular attention in the past decade because this method allows for the conversion of readily available N-heterocycles into potentially useful complex ring-expanded N-heterocycles, which are inaccessible by traditional methods. However, the catalytic asymmetric variant of this reaction has been rarely reported to date. Herein, we disclose an enantioselective one-carbon ring expansion reaction through chiral copper-catalyzed diyne cyclization, leading to the practical, atom-economic and divergent assembly of an array of valuable chiral N-heterocycles bearing a quaternary stereocenter in generally good to excellent yields with excellent enantioselectivities (up to >99% ee). This protocol represents the first example of asymmetric one-carbon ring expansion reaction of N-heterocycles based on alkynes.

The first-principles quantum chemical computations often scale as Nk (N = basis sets; k = 1-4 for linear scaling, Hartree-Fock or density functional theory methods), which makes the development of accurate pseudopotentials and efficient basis sets necessary ingredients in modeling of heavy elements such as lanthanides and actinides. Recently, we have developed 4f-in-core norm-conserving pseudopotentials and associated basis sets for the trivalent lanthanides [Lu et al., J. Chem. Theory Comput. 19, 82-96 (2023)]. In the present paper, we present a unified approach to optimize high-quality Gaussian basis sets for modeling and simulations of condensed-phase systems. The newly generated basis sets not only capture the low total energy and fairly reasonable condition number of overlap matrix of lanthanide-containing systems, but also exhibit good transferability and reproducibility. These advantages ensure the accuracy of the basis sets while avoiding linear dependency concern of atom-centered basis sets. The performance of the basis sets is further illustrated in lanthanide molecular and condensed-phase systems by using Gaussian-plane wave density functional approach of CP2K. These new basis sets can be of particular interest to model structurally complicated lanthanide molecules, clusters, solutions, and solid systems., (© 2024 Author(s). Published under an exclusive license by AIP Publishing.)

The oxidation state (OS) holds significant importance in the field of chemistry and serves as a crucial parameter for tracking electrons. Lanthanide (Ln) elements predominately exhibit a +III oxidation state, with a few elements such as Ce, Pr, Nd, Tb, and Dy able to achieve a +IV oxidation state. Over the past century, numerous attempts to synthesize Pr(V) have been made without success until recent reports on Pr(V) oxides and nitride-oxide in the gas phase expanded our understanding of Ln elements. However, the formation of Pr(V) in the condensed phase remains an open question. In this work, based on advanced quantum chemical investigations, we predict that formation of the solid-state CsPr V F 6 from Pr(III) and Pr(IV) complexes is exothermic, indicating that CsPr V F 6 is stable. The crystal structure comprises [PrF 6 ] - octahedral clusters occupying the interstitial spaces of Cs cations. Electronic structure analysis reveals that the CsPrF 6 crystal has a closed-shell structure and that Pr reaches its highest oxidation state of +V. The results indicate that the existence of Pr(V) in solid-state Ln fluorides is not impossible, which enriches our understanding of high-valence Ln compounds.

The dehydro-Diels-Alder (DDA) reaction is a powerful method for the construction of aromatic compounds. However, the enantioselective DDA reaction has been rarely developed, probably due to the competitive thermal reaction. Herein, we report a copper-catalyzed enantioselective DDA reaction through vinyl cation pathway. The reaction leads to the atom-economical synthesis of axially chiral phenyl and indolyl carbazoles in generally excellent yields with good to excellent atroposelectivities. This methodology represents the first example of non-noble metal-catalyzed enantioselective DDA reaction. Notably, new chiral ligand and organocatalyst derived from the constructed axially chiral carbazole are demonstrated to be useful in asymmetric catalysis., (© 2024 Wiley-VCH GmbH.)

Vinylidene ortho-quinone methides (VQMs) have been proven to be versatile and crucial intermediates in the catalytic asymmetric reaction in last decade, and thus have drawn considerable concentrations on account of the practical application in the construction of enantiomerically pure functional organic molecules. However, in comparison to the well established chiral Brønsted base-catalyzed asymmetric reaction via VQMs, chiral Brønsted acid-catalyzed reaction is rarely studied and there is no systematic summary to date. In this review, we summarize the recent advances in the chiral Brønsted acid-catalyzed asymmetric reaction via VQMs according to three types of reactions: a) intermolecular asymmetric nucleophilic addition to VQMs; b) intermolecular asymmetric cycloaddition of VQMs; c) intramolecular asymmetric cyclization of VQMs. Finally, we put forward the remained challenges and opportunities for potential breakthroughs in this area., (© 2024 Wiley-VCH GmbH.)

Transition metal-catalyzed epoxidation of carbonyl compounds through carbonyl ylides represents a highly effective method for synthesizing a diverse range of valuable epoxides. This review offers an in-depth overview of the latest developments in inter- and intramolecular epoxidation reactions involving metal carbenes and carbonyl compounds, encompassing both racemic to enantioselective transformations. These catalytic epoxidations are reviewed by highlighting their product selectivity, diversity and applicability, and the related mechanistic rationale is showcased where possible., (© 2024 Wiley-VCH GmbH.)

Background: Sepsis is a common and severe disease with a high mortality rate in intensive care unit (ICU). The hemoglobin (HGB) level is a key parameter for oxygen supply in sepsis. Although HGB is associated with the progression of inflammation in sepsis patients, its role as a marker following sepsis treatment remains unclear. Here, we studied the correlation between early temporal changes in HGB levels and long-term mortality rates in septic patients., Method: In this retrospective study of data on patients with sepsis from the Medical Information Mart for Intensive Care (MIMIC) IV database, the outcome was long-term mortality. Patients were divided based on the cut-off of the HGB percentage for receiver operating characteristic (ROC) curve calculation. Kaplan-Meier (KM) survival curves and Cox proportional hazards regression models were used to analyse the associations between groups and outcomes. Propensity score matching (PSM) was used to verify the results., Results: In this study, 2042 patients with sepsis and changes in HGB levels at day 4 after admission compared to day 1 were enrolled and divided into two groups: group 1 (n = 1147) for those with reduction of HGB < 7% and group 2 (n = 895) for those with dropping ≥ 7%. The long-term survival chances of sepsis with less than a 7% reduction in the proportion of HGB at day four were significantly higher than those of patients in the group with a reduction of 7% or more. After adjusting for covariates in the Cox model, the hazard ratios (HRs) with 95% confidence intervals (CIs) for long-term all-cause mortality in the group with a reduction of 7% or more were as follows: 180 days [HR = 1.41, 95% CI (1.22 to 1.63), P < 0.001]; 360 days [HR = 1.37, 95% CI (1.21 to 1.56), P < 0.001]; 540 days [HR = 1.35, 95% CI (1.20 to 1.53), P < 0.001]; 720 days [HR = 1.45, 95% CI (1.29 to 1.64), P < 0.001]. Additionally, the long-term survival rates, using Kaplan-Meier analysis, for the group with a reduction of 7% or more were lower compared to the group with less than 7% reduction at 180 days (54.3% vs. 65.3%, P < 0.001), 360 days (42.3% vs. 50.9%, P < 0.001), 540 days (40.2% vs. 48.6%, P < 0.001), and 720 days (35.5% vs. 46.1%, P < 0.001). The same trend was obtained after using PSM., Conclusion: A ≥ 7% decrease in HGB levels on Day 4 after admission was associated with worse long-term prognosis in sepsis patients admitted to the ICU., (© 2024. The Author(s).)

Catalytic cyclization of enynes is an efficient approach for the preparation of cyclic compounds, and a large variety of four- to six-membered rings could be synthesized using this method. However, it has been rarely employed for the construction of medium- and large-sized rings. Herein, we describe a copper-catalyzed cycloisomerization of ene-ynamides through a [2 + 2] cyclization/electrocyclic ring opening cascade, leading to the atom-economical assembly of indole-fused medium- and large-sized rings in moderate to excellent yields under mild reaction conditions. Importantly, the synthetic utility of this reaction was demonstrated by the convenient synthesis of iprindole.

A one-pot gold-catalyzed acyl migration followed by ytterbium-catalyzed asymmetric Friedel-Crafts alkylation is disclosed, leading to the rapid synthesis of chiral dihydrocarbazoles and dihydrodibenzofuran in generally moderate to good overall yields with good to excellent enantioselectivities. The gold-catalyzed acyl migration of propargyl acetates generates α-ylidene-β-diketones with high E / Z ratios, which are then subjected to the ytterbium-catalyzed asymmetric Friedel-Crafts alkylation without any purification. Importantly, this protocol provides a new type of substrate for asymmetric Friedel-Crafts alkylation.

Site- and stereoselective C-H functionalization is highly challenging in the synthetic chemistry community. Although the chemistry of vinyl cations has been vigorously studied in C(sp 3 )-H functionalization reactions, the catalytic enantioselective C(sp 3 )-H functionalization based on vinyl cations, especially for an unactivated C(sp 3 )-H bond, has scarcely explored. Here, we report an asymmetric copper-catalyzed tandem diyne cyclization/unactivated C(sp 3 )-H insertion reaction via a kinetic resolution, affording both chiral polycyclic pyrroles and diynes with generally excellent enantioselectivities and excellent selectivity factors (up to 750). Importantly, this reaction demonstrates a metal-catalyzed enantioselective unactivated C(sp 3 )-H functionalization via vinyl cation and constitutes a kinetic resolution reaction based on diyne cyclization. Theoretical calculations further support the mechanism of vinyl cation-involved C(sp 3 )-H insertion reaction and elucidate the origin of enantioselectivity., (© 2024. The Author(s).)

A gold-catalyzed, nucleophile-controlled cascade reaction of N -(2-azidophenyl-ynyl)methanesulfonamides with nitriles and water is described that provides structurally diverse 5 H -pyrimido[5,4- b ]indoles and 2-benzylidene-3-indolinones in good to excellent yields. Mechanistic studies indicate that the β-sulfonamido-α-imino gold carbene is the key intermediate which is generated through the gold-catalyzed cyclization of N -(2-azidophenyl-ynyl)methanesulfonamides and undergoes formal [4 + 2] cascade annulation with nitriles and intramolecular S N 2' type reaction with water, respectively.

Herein, we describe a Brønsted-acid-catalyzed enantioselective desymmetrization of 1,3-diols with alkynes through a hydroalkoxylation/hydrolysis process. The reaction leads to the atom-economical synthesis of valuable chiral β-amino alcohols under mild reaction conditions. Further synthetic transformations based on the β-amino alcohol moiety provide divergent approaches toward chiral N-containing heterocycles.

Here, an Ir/Zn-cocatalyzed atroposelective [2+2+2] cycloaddition of 1,6-diynes and ynamines was developed, forging various functionalized C─N axially chiral indoles and pyrroles in generally good to excellent yields (up to 99%), excellent chemoselectivities, and high enantioselectivities (up to 98% enantiomeric excess) with wide substrate scope. This cocatalyzed strategy not only provided an alternative promising and reliable way for asymmetric alkyne [2+2+2] cyclotrimerization in an easy handle but also settled the issues of previous [Rh(COD) 2 ]BF 4 -catalyzed system on the construction of C─N axial chirality such as complex operations, limited substrate scope, and low efficiency. In addition, control experiments and theoretical calculations disclosed that Zn(OTf) 2 markedly reduced the barrier of migration insertion to significantly increase reaction efficiency, which was distinctly different from previous work on the Lewis acid for improving reaction yield through accelerating oxidative addition and reductive elimination.

The enantioselective transformation of easily accessible 1,2-diketones represents a quick pathway towards enantioenriched molecules. Herein, we disclose a copper-catalyzed atroposelective formal [4+1] annulation of 1,2-diketones with vinyl cations, enabling the efficient and atom-economical construction of axially chiral arylpyrroles bearing 1,3-dioxole moieties with good to excellent enantioselectivities under mild reaction conditions. Importantly, this methodology constitutes the first enantioselective formal [4+1] annulation of 1,2-diketones.

The formal C-C bond insertion into aldehydes is an attractive methodology for the assembly of homologated carbonyl compounds. However, the homologation of aldehydes has been limited to diazo approach and the enantioselective reaction was rarely developed. Herein, we report an asymmetric formal C-C bond insertion into aldehydes through diyne cyclization strategy. In the presence of Cu(I)/SaBOX catalyst, this method leads to the efficient construction of versatile axially chiral naphthylpyrroles in moderate to excellent yields with good to excellent enantioselectivities. This protocol represents a rare example of asymmetric formal C-C bond insertion into aldehydes using non-diazo approach. The combined experimental and computational mechanistic studies reveal the reaction mechanism, origin of regioselectivity and stereoselectivity. Notably, the chiral phosphine ligand derived from synthesized axially chiral skeleton was proven to be applicable to asymmetric catalysis., (© 2023. The Author(s).)

One-carbon homologation reactions based on one-carbon insertion into the N-O bond of heterocycles have received tremendous interest over the past decades. However, these protocols have to rely on the use of hazardous and not easily accessible diazo compounds as precursors, and examples of the relevant asymmetric catalysis have not been reported. Here we show that a copper-catalyzed intermolecular formal (5 + 1) annulation of 1,5-diynes with 1,2,5-oxadiazoles involving one-carbon insertion into the heterocyclic N-O bond via non-diazo approach. This method enables practical and atom-economic synthesis of valuable pyrrole-substituted oxadiazines in generally moderate to good yields under mild reaction conditions. In addition, the possibility of such an asymmetric formal (5 + 1) annulation also emerges., (© 2023. Springer Nature Limited.)

Axially chiral biaryls widely exist in natural products and pharmaceuticals and are used as chiral ligands and catalysts in asymmetric synthesis. Compared to the well-established axially chiral 6-membered biaryl skeletons, examples of 5-membered biaryls have been quite scarce, and mono-substituted 3-arylpyrrole atropisomers have not been reported. Here, we disclose a copper-catalyzed atroposelective diyne cyclization for the construction of a range of axially chiral arylpyrrole biaryls in good to excellent yields with generally excellent enantioselectivities via oxidation and X-H insertion of vinyl cations. Importantly, this protocol not only represents the first synthesis of mono-substituted 3-arylpyrrole atropisomers, but also constitutes the first example of atroposelective diyne cyclization and the first atropisomer construction via vinyl cations. Theoretical calculations further support the mechanism of vinyl cation-involved cyclization and elucidate the origin of enantioselectivity., (© 2023 Wiley-VCH GmbH.)

Catalytic enantioselective transformation of alkynes has become a powerful tool for the synthesis of axially chiral molecules. Most of these atroposelective reactions of alkynes rely on transition-metal catalysis, and the organocatalytic approaches are largely limited to special alkynes which act as the precursors of Michael acceptors. Herein, we disclose an organocatalytic atroposelective intramolecular (4 + 2) annulation of enals with ynamides. This method allows the efficient and highly atom-economical preparation of various axially chiral 7-aryl indolines in generally moderate to good yields with good to excellent enantioselectivities. Computational studies were carried out to elucidate the origins of regioselectivity and enantioselectivity. Furthermore, a chiral phosphine ligand derived from the synthesized axially chiral 7-aryl indoline was proven to be potentially applicable to asymmetric catalysis., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Background: Uric acid, a formerly-known antioxidant that has recently been linked to numerous inflammatory diseases as a pro-inflammatory and -oxidative mediator in pathological conditions. It is imperative to reassess the association between periodontitis and uric acid locally and systematically. The aim of this systematic review was to systemically evaluate the association between periodontitis and the uric acid (UA) levels in blood, saliva and gingival crevicular fluid (GCF)., Methods: Relevant clinical studies up to January 28, 2023 were identified and retrieved from electronic databases including PubMed, Scopus, EMBASE and Web of Science, with periodontitis, uric acid, hyperuricemia and gout as the keywords. The weighted (WMD) or standardized mean difference (SMD) was calculated using fixed- or random-effect models. Methodological heterogeneity was assessed., Results: Sixteen eligible observational studies and one RCT were enrolled, which included 1354 patients with periodontitis and 989 controls. Three sample types for UA detection were involved, including blood (n = 8), saliva (n = 9) and GCF (n = 1). Meta-analysis demonstrated an enhanced plasma UA concentration (WMD = 1.00 mg/dL, 95% CI 0.63 to 1.37, P < 0.001) but a decreased salivary UA level (SMD = -0.95, 95% CI -1.23 to -0.68, P < 0.001) in periodontitis versus control. Statistical heterogeneity among the plasma- and saliva-tested studies were moderate (I 2  = 58.3%, P = 0.066) and low (I 2  = 33.8%, P = 0.196), respectively., Conclusions: Within the limitations of the enrolled studies, it seems that there is an association between periodontitis and increased blood UA and decreased salivary UA. (Registration no. CRD42020172535 in Prospero)., (© 2023. The Author(s).)

In the past two decades, substantial advances have been made on the asymmetric alkyne functionalization by the activation of inert alkynes. However, these asymmetric transformations have so far been mostly limited to transition metal catalysis, and chiral Brønsted acid-catalyzed examples are rarely explored. Here, we report a chiral Brønsted acid-catalyzed dearomatization reaction of phenol- and indole-tethered homopropargyl amines, allowing the practical and atom-economical synthesis of a diverse array of valuable fused polycyclic enones and indolines bearing a chiral quaternary carbon stereocenter and two contiguous stereogenic centers in moderate to good yields with excellent diastereoselectivities and generally excellent enantioselectivities (up to >99% enantiomeric excess). This protocol demonstrates Brønsted acid-catalyzed asymmetric dearomatizations via vinylidene-quinone methides.

A copper-catalyzed oxidative cyclization of alkenyl N -propargyl ynamides is described. This protocol enables the practical synthesis of diverse spirocyclic γ-lactams bearing an exocyclic double bond with generally high Z / E selectivity in moderate to good yields. Importantly, this copper-catalyzed oxidative cyclization demonstrates a distinctive selectivity in comparison with the related gold catalysis.

The functionalization of etheric C-O bonds via C-O bond cleavage is an attractive strategy for the construction of C-C and C-X bonds in organic synthesis. However, these reactions mainly involve C(sp 3 )-O bond cleavage, and a catalyst-controlled highly enantioselective version is extremely challenging. Here, we report a copper-catalyzed asymmetric cascade cyclization via C(sp 2 )-O bond cleavage, allowing the divergent and atom-economic synthesis of a range of chromeno[3,4- c ]pyrroles bearing a triaryl oxa-quaternary carbon stereocenter in high yields and enantioselectivities. Importantly, this protocol not only represents the first [1,2]-Stevens-type rearrangement via C(sp 2 )-O bond cleavage, but also constitutes the first example of [1,2]-aryl migration reactions via vinyl cations., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

[2,3]-Sigmatropic rearrangement reaction involving sulfonium ylide (Doyle-Kirmse reaction) generated from metal carbenes represents one of the powerful methods for the construction of C(sp 3 )-S and C-C bonds. Although significant advances have been achieved, the asymmetric versions via the generation of sulfonium ylides from metal carbenes have been rarely reported to date, and they have so far been limited to diazo compounds as metal carbene precursors. Here, we describe a copper-catalyzed enantioselective Doyle-Kirmse reaction via azide-ynamide cyclization, leading to the practical and divergent assembly of an array of chiral [1,4]thiazino[3,2-b]indoles bearing a quaternary carbon stereocenter in generally moderate to excellent yields and excellent enantioselectivities. Importantly, this protocol represents a unique catalytic asymmetric Doyle-Kirmse reaction via a non-diazo approach and an unprecedented asymmetric [2,3]-sigmatropic rearrangement via α-imino metal carbenes., (© 2023 Wiley-VCH GmbH.)

Herein, an I 2 -catalyzed unprecedented cycloisomerization of ynamides is developed, furnishing various functionalized bis(indole) derivatives in generally good to excellent yields with wide substrate scope and excellent atom-economy. This protocol not only represents the first molecular-iodine-catalyzed tandem complex alkyne cycloisomerizations, but also constitutes the first chemoselective cycloisomerization of tryptamine-ynamides involving distinctively different C(sp 3 )-C(sp 3 ) bond cleavage and rearrangement. Moreover, chiral tetrahydropyridine frameworks containing two stereocenters are obtained with moderate to excellent diastereoselectivities and excellent enantioselectivities. Meanwhile, cycloisomerization and aromatization of ynamides produce pyrrolyl indoles with high efficiency enabled by I 2 . Additionally, control experiments and theoretical calculations reveal that this reaction probably undergoes a tandem 5-exo-dig cyclization/rearrangement process., (© 2022 Wiley-VCH GmbH.)

Carbonyl ylides have proven to be powerful synthons for the efficient construction of various valuable O-heterocycles, and the formation of carbonyl ylides by the reaction of metal carbenes with carbonyls has attracted increasing attention over the past decades. However, a catalyst-controlled highly enantioselective reaction of carbonyl ylides from metal carbenes is extremely challenging. Herein, we report a novel copper-catalyzed asymmetric formal [2+1] and [4+1] annulations of diynes with ketones via carbonyl ylides. Importantly, this protocol not only represents the first example of successful asymmetric epoxidation via carbonyl ylides, but also constitutes the first reaction of vinyl cations with carbonyl compounds. This method leads to the divergent, practical and atom-economical synthesis of a range of chiral oxiranes and dihydrofurans in moderate to excellent yields with generally excellent enantioselectivities and diastereoselectivities via remote-stereocontrol strategy., (© 2022 Wiley-VCH GmbH.)

Herein, an unprecedented non-noble-metal-catalyzed oxidation/cyclization of ene-ynamides is developed, allowing the synthesis of diversely functionalized lactams in moderate to good yields with excellent diastereoselectivities without the observation of typical cyclopropanation products. In combination with Ellman's tert -butylsulfinimine chemistry, chiral γ-lactams containing three contiguous stereocenters are obtained with high diastereo- and enantioselectivity. Moreover, density functional theory (DFT) calculations indicate that this protocol probably undergoes a carbon cation or proton transfer process.

Medium-sized N,S-heterocycles have received tremendous interest due to their biological activities and potential medical applications. However, asymmetric synthesis of these compounds are extremely rare. Described herein is a catalyst-dependent [3,3]-sigmatropic rearrangement of sulfoxide-ynamides, enabling divergent and atom-economic synthesis of a series of valuable medium-sized N,S-heterocycles in moderate to good yields with broad substrate scope. Importantly, excellent enantioselectivities have been achieved via an unprecedented chirality-transfer. Moreover, theoretical calculations are employed to elucidate the origins of the catalyst-dependent stereospecific [3,3]-rearrangement., (© 2022 Wiley-VCH GmbH.)

A thrust stand is developed for testing micro-Newton level thrusters on the ground. The stand is composed of a compound pendulum that is symmetrically suspended by two thin beryllium copper strips, and it is precisely calibrated by gravity. The stiffness of the stand can be adjusted in 3 orders of magnitude by a counterweight. When the stiffness is larger than 1 Nm/rad, the stand demonstrates a fast response to thrust. The measured range of the stand reaches 1000 μN, and the noise is less than 0.1 μN/Hz within 1 mHz-1 Hz. To calibrate the resolution of the stand, an electrostatic force is applied to the stand with an actuator. The equivalent thrust is determined to be 0.09 μN with a standard uncertainty of 0.02 μN. Using the stand, a micro-Newton colloid thruster is tested. The output of the colloid thruster changes with the applied voltage as 0.015(1) μN/V. When changing the voltage by 50 V, the change in thrust is measured to be 0.7 μN with a standard uncertainty of 0.1 μN.

In recent years, asymmetric catalysis of ynamides has attracted much attention, but these reactions mostly constructed central chirality, except for a few examples on the synthesis of axially chiral compounds which exclusively relied on noble-metal catalysis. Herein, a facile access to axially chiral N-heterocycles enabled by chiral Brønsted acid-catalyzed 5-endo-dig cyclization of ynamides is disclosed, which represents the first metal-free protocol for the construction of axially chiral compounds from ynamides. This method allows the practical and atom-economical synthesis of valuable N-arylindoles in excellent yields with generally excellent enantioselectivities. Moreover, organocatalysts and ligands based on such axially chiral N-arylindole skeletons are demonstrated to be applicable to asymmetric catalysis., (© 2022 Wiley-VCH GmbH.)

Significant advances have been achieved for the construction of chiral skeletons containing 1,2,3-triazoles via transition-metal-catalyzed asymmetric azide-alkyne cycloaddition; however, most of them have been limited to terminal alkynes in the synthesis of central chirality via desymmetrization and dynamic/dynamic kinetic resolution. Enantioselective transition-metal-catalyzed azide-internal-alkyne cycloaddition is extremely limited. Moreover, the construction of a challenging five-membered (hetero)biaryl axially chiral molecule via transition-metal-catalyzed asymmetric azide-internal-alkyne cycloaddition is still underexplored. Herein, we first report an atroposelective and atom-economical synthesis of axially chiral 1,4,5-trisubstituted 1,2,3-triazoles, directly acting as core chiral units of challenging five-membered atropisomers, via the enantioselective Rh-catalyzed azide-alkyne cycloaddition (E-RhAAC) of internal alkynes and azides. The reaction demonstrates excellent functional group tolerance, forging a variety of C-C axially chiral 1,2,3-triazoles under mild conditions with moderate to excellent yields (up to 99% yield) and generally high to excellent enantioselectivities (up to 99% ee) along with specific regiocontrol. The origin of regio- and enantioselectivity control is disclosed by density functional theory (DFT) calculations, providing new guidance for the facile construction of axially chiral compounds.

Here, we report a copper-catalyzed asymmetric cascade cyclization/[1,2]-Stevens-type rearrangement via a non-diazo approach, leading to the practical and atom-economic assembly of various valuable chiral chromeno[3,4-c]pyrroles bearing a quaternary carbon stereocenter in generally moderate to good yields with wide substrate scope and excellent enantioselectivities (up to 99 % ee). Importantly, this protocol not only represents the first example of catalytic asymmetric [1,2]-Stevens-type rearrangement based on alkynes but also constitutes the first asymmetric formal carbene insertion into the Si-O bond., (© 2021 Wiley-VCH GmbH.)

Transition-metal-catalyzed Si-H bond insertion reactions are generally limited to stabilized diazo compounds. An efficient copper-catalyzed Si-H bond insertion reaction of N -propargyl ynamides with hydrosilanes is described, allowing practical and atom-economic construction of valuable organosilanes in generally moderate to excellent yields under mild reaction conditions. Notably, this reaction constitutes a new method of Si-H bond insertion reaction involving vinyl cations as key intermediates.

Described herein is a novel Brønsted acid catalyzed intramolecular hydroalkoxylation/Claisen rearrangement, allowing the practical and atom-economic synthesis of a range of valuable spirolactams from readily available ynamides in generally good to excellent yields with excellent diastereoselectivities and broad substrate scope. Importantly, an unexpected dearomatization of nonactivated arenes and heteroaromatic compounds is involved in this tandem sequence. Moreover, an asymmetric version of this tandem cyclization was also achieved by efficient kinetic resolution by chiral phosphoric acid catalysis. In addition, the [3,3]-rearrangement is shown to be kinetically preferred over the related [1,3]-rearrangement by theoretical calculations., (© 2021 Wiley-VCH GmbH.)

Chiral Brønsted acid-catalysed asymmetric synthesis has received tremendous interest over the past decades, and numerous efficient synthetic methods have been developed based on this approach. However, the use of chiral Brønsted acids in these reactions is mostly limited to the activation of imine and carbonyl moieties, and the direct activation of carbon-carbon triple bonds has so far not been invoked. Here we show that chiral Brønsted acids enable the catalytic asymmetric dearomatization reactions of naphthol-, phenol- and pyrrole-ynamides by the direct activation of alkynes. This method leads to the practical and atom-economic construction of various valuable spirocyclic enones and 2H-pyrroles that bear a chiral quaternary carbon stereocentre in generally good-to-excellent yields with excellent chemo-, regio- and enantioselectivities. The activation mode of chiral Brønsted acid catalysis revealed in this study is expected to be of broad utility in catalytic asymmetric reactions that involve ynamides and the related heteroatom-substituted alkynes., (© 2021. The Author(s), under exclusive licence to Springer Nature Limited.)

An efficient copper-catalyzed cyclization of N -propargyl ynamides with borane adducts through B-H bond insertion has been developed. A series of valuable organoboron compounds are constructed in generally good yields with a wide substrate scope and good functional group tolerance under mild reaction conditions. Importantly, this protocol via vinyl cation intermediates constitutes a novel way of B-H bond insertion.

Catalytic transformations involving metal carbenes are considered one of the most important aspects of homogeneous transition metal catalysis. Recently, gold-catalyzed generation of gold carbenes from readily available alkynes represents a significant advance in metal carbene chemistry. This Review summarizes the advances in the gold-catalyzed nitrene-transfer reactions of alkynes with nitrogen-transfer reagents, such as azides, nitrogen ylides, isoxazoles, and anthranils, and gold-catalyzed carbene-transfer reactions, involving oxygen atom-transfer reactions of alkynes with nitro compounds, nitrones, sulfoxides, and pyridine N -oxides, through the presumable α-imino gold carbene and α-oxo gold carbene intermediates, respectively. Gold-catalyzed processes are reviewed by highlighting their product diversity, selectivity, and applicability, and the mechanistic rationale is presented where possible.

Metal carbenes have proven to be one of the most important and useful intermediates in organic synthesis, but catalytic asymmetric reactions involving metal carbenes are still scarce and remain a challenge. Particularly, the mechanistic pathway and chiral induction model in these asymmetric transformations are far from clear. Described herein is a copper-catalyzed asymmetric cyclization of alkenyl diynes involving a vinylic C(sp 2 )-H functionalization, which constitutes the first asymmetric vinylic C(sp 2 )-H functionalization through cyclopentannulation. Significantly, based on extensive mechanistic studies including control experiments and theoretical calculations, a revised mechanism involving a novel type of endocyclic copper carbene via remote-stereocontrol is proposed, thus providing new mechanistic insight into the copper-catalyzed asymmetric diyne cyclization and representing a new chiral control pattern in asymmetric catalysis based on remote-stereocontrol and vinyl cations. This method enables the practical and atom-economical construction of an array of valuable chiral polycyclic-pyrroles in high yields and enantioselectivities., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

An efficient regio- and diastereoselective method for the construction of valuable trans-3,4-diaryldihydrocoumarins via metal-free [4+2] annulation of ynamides with o-hydroxybenzyl alcohols has been developed. Ynamides are first treated as 2-π partners to react with o-hydroxybenzyl alcohols via traceless sulfonamide directing groups, affording trans-3,4-diaryldihydrocoumarins in good yields with high regio- and diastereoselectivities. This metal-free methodology is also characterized by a wide substrate scope, good functional group tolerance, and efficiency on a gram scale.

Ynamides are electron-rich heteroatom-substituted alkynes with C-C triple bond directly tethered to the amide group. Over the past decades, ynamides have proven to be versatile reagents for organic synthesis and have received extensive attention. Compared with the well-established ionic reactions of ynamides, radical-based ynamide reactions have been exploited relatively seldom. Herein, radical reactions of ynamides, classified by radical attack at the α-position and β-position of ynamides, are reviewed by highlighting the reaction selectivity, scope, mechanism, and applicability. The aim of this review is to provide a comprehensive summarization of these advances, casting light on the further development of ynamide chemistry., (© 2020 Wiley-VCH GmbH.)

Over the past two decades, the development and application of ynamide chemistry have received more and more attention. Ynamides have proven to be versatile reagents for organic synthesis, and have been widely applied to the rapid assembly of a diverse range of structurally complex N-containing molecules, especially the valuable N-heterocycles. In comparison with the well-established transition metal-catalyzed reactions of ynamides, metal-free ynamide transformations have relatively seldom been exploited. Recently, Brønsted acid-mediated reactions of ynamides represent significant advances in ynamide chemistry. This review summarizes the latest trends and developments of Brønsted acid-mediated reactions of ynamides, including cycloaddition, cyclization, intramolecular alkoxylation-initiated rearrangement, oxygen atom transfer reactions and hydro-heteroatom addition reactions.

Here an efficient copper-catalyzed cascade cyclization of azide-ynamides via α-imino copper carbene intermediates is reported, representing the first generation of α-imino copper carbenes from alkynes. This protocol enables the practical and divergent synthesis of an array of polycyclic N-heterocycles in generally good to excellent yields with broad substrate scope and excellent diastereoselectivities. Moreover, an asymmetric azide-ynamide cyclization has been achieved with high enantioselectivities (up to 98:2 e.r.) by employing BOX-Cu complexes as chiral catalysts. Thus, this protocol constitutes the first example of an asymmetric azide-alkyne cyclization. The proposed mechanistic rationale for this cascade cyclization is further supported by theoretical calculations., (© 2020 Wiley-VCH GmbH.)

ConspectusYnamides are electron-rich heteroatom-substituted alkynes with a C-C triple bond directly attached to the amide group. Importantly, this amide group is able to impose an electronic bias, thus resulting in the highly regioselective attack of this polarized alkyne by a large variety of nucleophiles. Over the past two decades, catalytic reactions of ynamides have experienced dramatic developments, especially those catalyzed by transition metals. As a result, ynamides have been widely applied to the rapid and efficient assembly of versatile structurally complex N-containing molecules, especially in an atom-economic and stereoselective way.On the basis of newly developed ynamide preparations and new alkyne transformations, we first developed oxidation-initiated tandem reactions of ynamides such as zinc-catalyzed ynamide oxidation/C-H functionalization and copper-catalyzed ynamide oxidation/carbene metathesis, leading to divergent synthesis of isoquinolones, β-carbolines, and pyrrolo[3,4- c ]quinolin-1-ones. Importantly, this protocol represents the first non-noble-metal-catalyzed intermolecular oxidation of alkynes by N -oxide type oxidants, and the related overoxidation could be dramatically inhibited in this non-noble-metal catalysis. Then, we achieved gold-catalyzed amination-initiated tandem reactions of ynamides via α-imino gold carbenes for efficient construction of various 2-aminoindoles, 3-amino-β-carbolines, and 2-aminopyrroles, where two new types of nitrene transfer reagents (benzyl azides and isoxazoles) were discovered. In particular, the use of isoxazoles as nitrene transfer reagents for atom-economic generation of α-imino metal carbenes has also been elegantly exploited by Hashmi, Liu, and many other groups, providing ready access to a wide range of functionalized N-heterocycles. Moreover, we revealed that donor/donor copper carbenes could be generated via copper-catalyzed diyne cyclization under mild conditions. These novel copper carbenes could undergo asymmetric C-H insertion, cyclopropanation, and formal [3 + 2] cycloaddition to produce diverse chiral polycyclic pyrroles with good to excellent enantioselectivities. Thus, this strategy may open new avenues in catalytic asymmetric reaction of ynamides, which remain largely unexplored and deserve more attention. Meanwhile, we also accomplished the efficient and practical synthesis of medium-sized lactams by yttrium-catalyzed cascade cyclization of allyl alcohol-tethered ynamides and the combination of radical chemistry based on visible-light photoredox catalysis with ynamide chemistry for divergent synthesis of useful 2-benzhydrylindoles and 3-benzhydrylisoquinolines.In this Account, we describe a panoramic picture of our recent contributions since 2015 to the development and application of ynamide chemistry in organic synthesis via transition metal-catalyzed tandem reactions by focusing on the tetrafunctionalization of ynamides. These studies provide not only efficient and attractive methods for divergent synthesis of valuable N-heterocycles but also some new insights into the exploration of alkyne chemistry and metal carbene chemistry.