Cationic chiral Au(I) complexes catalyze asymmetric Pictet–Spengler reactions between tryptamines and arylaldehydes. The resulting tetrahydro-β-carbolines are obtained with wide functional group tolerance in high yield enantioselectivities (up to 95%). Aldehydes bearing polar or protic functions well tolerated. reaction features a hitherto unknown C2-auration of the indole as key step, supported by density theory calculations.

A three-component Pd-catalyzed coupling of ynamides, aryl diazonium salts, and boronic acids for the synthesis novel triaryl-substituted enamides is described. This transformation represents first example an umpolung regioselective unsymmetrical syn-1,2-diarylation/aryl-olefination ynamides. The moieties salt (electrophile) acid (nucleophile) are explicitly incorporated in electrophilic α- nucleophilic β-position, respectively, ynamide, resulting a single isomer N-bearing tetrasubstituted...

Abstract π-Extended tetrasubstituted olefins are widely found motifs in natural products, leading drugs, and agrochemicals. Thus, development of modular strategies for the synthesis complex all-carbon-substituted always draws attention. The difunctionalization unsymmetrical alkynes is an attractive approach but it has remained faced with regioselectivity issues. Here we report discovery a regio- stereoselective syn -1,2-dicarbofunctionalization internal alkynes. A cationic Pd-catalyzed...

α-Fluoro-α′-aryl ketones are crucial in pharmaceuticals and agrochemicals. However, synthesizing unsymmetrical α-fluoro-α′-aryl poses regioselective challenges. This study presents a one-pot aryl-oxy-fluorination method for such fluoro-aryl ketones. Using ynamide, aryl boronic acid, F-source under Pd-catalysis, this efficiently produces wide range of valuable with potential applications. Through combination control experiments DFT studies, we proposed reaction mechanism involving situ acetic...

Higher-order cycloadditions are a simple and effective strategy for constructing significant medium-sized architectures. Azaheptafulvenes reacting with readily accessible bicyclo[1.1.0]butanes (BCBs) through FeCl3-promoted intermolecular formal [8π+2σ] cycloaddition reactions to access cycloheptatriene-fused 2-azabicyclo[3.1.1]heptanes have been developed. This new reaction tolerated wide range of azaheptafulvenes BCBs. Furthermore, the amplification experiment synthetic transformations...

We report an efficient intramolecular hydroacyloxylation of unactivated alkenes, offering a streamlined access to relevant γ-lactones, which features the utilization either calcium(II) salt or triflimide as catalyst in hexafluoroisopropanol. This method could be applied synthesis natural products and late-stage functionalization bioactive molecules. Additionally, DFT computations were used elucidate twist reactivity observed between hydroamidation alkenes regarding formation 5- 6-membered rings.

A cationic palladium-catalyzed arylalkenylation of ynamides is presented. The putative keteniminium arylpalladium intermediate likely dictates the regioselective carbopalladation ynamide to form a vinylpalladium species. capture this complex by olefin yields linear conjugated β-alkenyl aminodienes (especially with trans selectivity). transformation features broad scope labile functional group tolerance and makes 42 unusual molecular scaffolds structural diversity. DFT studies provide...

A Pd-catalyzed site-selective C(sp2)–H activation/cycloimidoylation of 2-isocyano-2,3-diarylpropanoates to construct diverse cyclic imine products has been developed. Six-membered 3,4-dihydroisoquinolines containing a C3 quaternary carbon center were generated dominantly by using bulky Ad2Pn-Bu as ligand, while five-membered 1,1-disubstituted 1H-isoindoles formed preferentially in the presence bidentate phosphine ligand DPPB. The selectivity for 1H-isoindole formation was enhanced steric...

The GaCl3-mediated Friedel–Crafts alkylation of benzene by methyl chloride has been studied means density functional theory computations at the M062X/6-311+G(2d,2p) level theory. role superelectrophilic Ga2Cl6 homodimers confirmed and explained. results are consistent with observation second-order rate dependence in alkylations. This work also reveals that, even a typical alkylation, no Wheland-type σ-complex can be modeled, suggesting concerted electrophilic aromatic substitution. Also...

Reported herein is a <italic>syn</italic>-thioallylation of ynamides incorporating sulfide moiety at the α-position and an allyl group β-position ynamide.

A density functional theory (DFT) study has been conducted to elucidate the mechanism of rhodium(III)-catalyzed C–H activation O-substituted N-hydroxybenzamides and cyclohexadienone-containing 1,6-enynes. The impact different internal oxidants (OPiv versus OMe) on arylative cyclization (i.e., Ⓝ-Michael addition Ⓒ-Michael addition) evaluated in detail. pathway proceeded via a Rh(I) species, while Rh(III) remained unchanged throughout pathway. Rh(III)/Rh(I) catalytic cycle was from those...

Martin and co-workers recently developed a strategy for Ni(0)-complex-catalyzed [4 + 4] annulation of primary benzocyclobutenones (BCBs) 1,3-dienes. A density functional theory study was performed to clarify the catalytic mechanism. The results provide insights into origins chemo-, regio-, diastereoselectivity. calculation explain why only P(C6H5CF3)3, among several candidates, well BCB with 1,3-diene achieved Ni(0) but not Rh(I) catalyst.

An efficient ortho-C-alkylation of unprotected anilines with a variety styrenes and alkenes using univalent cationic indium(I) catalyst is reported. Mechanistic studies revealed that the reaction likely proceeds via tandem hydroamination/Hofmann–Martius rearrangement. The high compatibility between complex primary led us to develop an In(I)+-catalyzed hydroamination secondary alkenylamines. Computations support catalytic activity naked In(I)+ ions, outer sphere mechanism for C–N bond...

Abstract A three‐component Pd‐catalyzed coupling of ynamides, aryl diazonium salts, and boronic acids for the synthesis novel triaryl‐substituted enamides is described. This transformation represents first example an umpolung regioselective unsymmetrical syn ‐1,2‐diarylation/aryl‐olefination ynamides. The moieties salt (electrophile) acid (nucleophile) are explicitly incorporated in electrophilic α‐ nucleophilic β‐position, respectively, ynamide, resulting a single isomer N‐bearing...

Li and co-workers recently developed a dual C–H bond activation strategy, using Rh(III) catalyst, for [3 + 2]/[5 2] annulation of primary 4-aryl-1,2,3-triazoles alkynes. The Rh(III)-catalyzed alkynes is challenging because only single achieved Rh(II) Ni(0) catalysts. Intrigued by the novel we performed density functional theory study to unravel this activation. A Friedel–Crafts type mechanism proved be more favorable than concerted metalation–deprotonation (CMD) first second proceeded via...

A fundamental understanding of biomass-based transformation furfural (1a) to 2-furamide (4a) is highly desirable for the extension amide chemistry. In this research, direct amidation 1a with hydroxylamine 4a was investigated by using a Cu-doped Co3O4 (Cu/Co3O4) catalyst 2-furancarboxaldehyde oxime (2a) and 2-furonitrile (3a) as detectable intermediates. Mechanism research has demonstrated presence two competitive, independent, parallel reaction pathways: (i) 2a-to-4a rearrangement (the...

To explore the influencing factors of Yang deficiency constitution in traditional Chinese medicine (TCM) from perspective mathematics with use calculation formulas, so as to protect patients getting diseases caused by and provide suggestions for TCM disease prevention. Based on classification determination criteria implemented China Association Medicine, data 24 solar terms May 5, 2020 (Start Summer) April 20, 2021 (Grain Rain) identification were collected mobile system. The grey...

To study the influencing factors of blood stasis constitution and provide a basis for treating stasis-related diseases by traditional Chinese medicine (TCM) identification. Data were collected using self-developed TCM identification platform based on B/S model project team. The obtained data divided into normal groups. differences categorical type (gender, birth mode, feeding mode within four months birth, family history, marital status, eating habits, sleeping exercise emotional state,...

The concept of alkynophilicity is revisited with group 13 MX3 metal salts (M = In, Ga, Al, B; X Cl, OTf) using M06-2X/6-31+G(d,p) calculations. This study aims at answering why some these show reactivity toward enynes that similar to observed late-transition-metal complexes, notably Au(I) species, and them are inactive. For this purpose, the mechanism skeletal reorganization 1,6-enynes into 1-vinylcyclopentenes has been computed, including monomeric ("standard") dimeric (superelectrophilic)...

The mechanism of the calcium-catalyzed coupling alcohols with vinylboronic acids has been analyzed by means density functional theory computations. This study reveals that calcium and boron Lewis associate to form a superelectrophile able promote pericyclic group transfer reaction allyl alcohols. With other alcohols, two act synergistically activate OH functionality trigger SNi pathway. These mechanisms are affected nature counterions, which rationalized electronic steric factors.

The asymmetric Michael addition reaction of guaiazulene to α,β-unsaturated 2-acyl imidazoles has been developed with a chiral-at-metal Rh(III) complex as catalyst for the first time. corresponding adducts were obtained...

The metal-catalyzed remote C–H functionalization of quinoline N-oxide was investigated systematically through density functional theory calculations. We found that the coordination moiety to a metal center greatly lowered barrier activation and made C8–H favorable, regardless (Ir, Rh, or Pd). For IrIII RhIII systems, active catalyst identified from several candidates as [Cp*M(OAc)]+ (M = Ir Cp* pentamethylcyclopentadienyl) because in can coordinate system. cleavage bond favored over C2–H...