Intramolecular Dehydration Research Articles

Visible-Light-Induced [4+1] Cyclization-Aromatization of Acylsilanes and α,β-Unsaturated Ketones

Visible-Light-Induced [4+1] Cyclization-Aromatization of Acylsilanes and α,β-Unsaturated Ketones

Insights into CQDs-doped perylene diimide photocatalysts for the degradation of naproxen

Advanced efficacious catalytic technologies have the capacity to enhance the degradation of emerging anthropogenic contaminants. Herein, the supramolecular nanofibers, namely carbon quantum dots doped perylene diimide (PDI/CQDs), was prepared via a one-step acidification polymerization method. The results showed that the rate constants of naproxen (NPX) were of 3.50 times in contrast to pristine PDI. When the doping amount of CQDs on PDI was 2%, the half-life of NPX was only 0.66 min in the PDI/CQDs photocatalytic system. The main active substances in the photocatalytic degradation of NPX were h+, O2•−, 1O2, H2O2 and •OH. Degradation mainly occurred through four paths, including the decarboxylation reaction, classical Ipso-substitution reaction, electron-dominated reaction, and intramolecular dehydration reaction paths. The obvious inhibitory effects of HA, Cl−, NO2– and HCO3– was observed, where a lower pH value was beneficial for the degradation of NPX. An overall mechanism was proposed through Density Functional Theory calculations of high-efficiency electron-hole separation of PDI/CQDs. To improve the nanomaterial applicability, PDI/CQDs cellulose acetate membrane was synthesized and used under different water conditions, which further revealed the stability and efficient of this membrane. Ultimately, the aggregate results provided basic supportive data for the remediation of contaminants in water and wastewater.

Study of the molecular-structural composition of alcoholic extracts of radio-induced potato tubers by mass spectrometry and EPR

This article presents data on electron paramagnetic resonance (EPR) and mass spectrometric analysis of potato tubers, irradiated with gamma rays, in order to examine and identify changes in the molecular composition of organic matter following radiation exposure. The products of the Maillard reaction were compared with the products of intramolecular radiolysis of organic constituents of potatoes. The presence of free radicals was verified using EPR. DDPM (2,3-dihydro-3,5-dihydroxy-6-methyl-4 (H) -pyran-4-one) was among the radiolysis products detected via mass spectrometry, which points to the intramolecular dehydration of potato carbohydrates. EPR signals indicate single-electron transitions of the semidione radical anionic molecular compounds. It has been shown that irradiation with gamma rays significantly destroys the carbohydrate, lipid, keto-carotene and amino acid molecules of potatoes.

Solvent-Induced Selectivity of Isoprene From Bio-Derived Prenol.

In this work we demonstrate the selective catalytic conversion of prenol, which is an allylic alcohol that can be prepared from renewable resources to isoprene. The catalyst is an inexpensive molybdenum complex (Molyvan L) designed and used as an additive for lubricants. Isoprene is generated under relatively mild reaction parameters at 130–150°C, for 2 h, under vapor pressure conditions that do not exceed 50 psi. Two cases were studied: one in which Molyvan L was dissolved in a base oil at 1% concentration (weight/weight) and then mixed with a solvent and prenol and the other in which neat Molyvan L was introduced in the reaction and the base oil was replaced with the solvent and prenol. We investigated the selectivity of the reaction using the following solvents in both cases: dodecane, dodecanol, isododecane, octane, blendstock for oxygenate blending (BOB3), a fuel surrogate, a polyalphaolefin (PAO4), and methoxy polyethylene glycol (methoxy PEG350). Although conversion of prenol was above 94% in all experiments, isoprene was formed with various degrees of efficiency alongside a prenol isomeric alcohol, diprenyl ether and mixed ether via intramolecular and intermolecular dehydration reactions. Dodecane appeared to have the highest level of selectivity initially in base oil so we studied the effect of various dodecane-like solvents on isoprene yield and product profile. Surprisingly, octane (similar to dodecane) and isododecane (branched alkane) generated insignificant amounts of byproducts, essentially providing the highly desired isoprene with a very high selectivity. Branching of the solvent does not appear to have an effect on selectivity. Another advantage of this catalyst is the low loadings required to effect the transformation; that is, 0.25% (weight/volume) in the cases using neat Molyvan L and 0.5% (weight/volume) in the cases using Molyvan L dissolved in the base oil. Provided that prenol can be produced in large scale from bioresources, this work would enable the sustainable production of isoprene, in good yield, and with very high selectivity.

Anti-COVID-19 and antidiabetic activities of new oleanane and ursane-type triterpenoids from Salvia grossheimii: an in-silico approach

Salvia grossheimii is a perennial herb with antidiabetic and cytotoxic constituents. In continuation of our study on S. grosshiemii to identify the bioactive phytochemicals, we have reported the characterization of seven undescribed triterpenoids. The aerial parts of the plant were extracted in dichloromethane and its constituents were isolated using chromatography techniques. The structures of compounds were identified using 1D, 2D NMR, and ESI-MS spectral data. Seven new oleanane- and ursane-type triterpenoids (1–7) were identified in S. grossheimii. The structures of 1–7 were characterized as; 2α-hydroxy-3β-acetoxy-olean-9(11),12-diene (1), 2α-acetoxy-3β-hydroxy-olean-9(11),12-diene (2), 3β-acetoxy-olean-18-ene,2α,11α-diol (3), 2α-hydroxy-3β-acetoxy-urs-9(11),12-diene (4), 2α-acetoxy-3β-hydroxy-urs-9(11),12-diene (5), 2α,3β-diacetoxy-urs-12-ene-11α,20β-diol (6), 2α,3β-diacetoxy-urs-9(11),12-diene-20β-ol (7). Triterpenoids (2, 5, and 7) were intramolecular transesterification or dehydration products of their corresponding isomers or allylic alcohol in the C rings, respectively, produced in-situ during NMR spectroscopy. Virtual screening of 1–7 was performed with molecular docking analysis to identify the potential SARS-CoV-2 and α-glucosidase inhibitors using the smina molecular docking algorithm. The best binding energy values (kcal/mol) against COVID-19 main protease Mpro were calculated for 6 (-8.77) and 7 (-8.68), and the higher binding affinities toward human α-glucosidase were obtained for 2 (-9.39) and 6 (-8.63). This study suggests S. grossheimii as a rich source of bioactive triterpenoids and introduces new natural compounds. Considering the high binding energy values of 2, 6, and 7, these structures could be candidates for anti-COVID-19 and antidiabetic drug development in the future.

Microwave pyrolysis of biomass model compounds for bio-oil: Formation mechanisms of the nitrogenous chemicals and DFT calculations

Microwave pyrolysis of nitrogen-rich biomass for bio-oil is a green and sustainable pathway to realize energy conversion and produce high-value nitrogenous chemicals. This work selected three typical amino acids (serine (Ser), glutamic acid (Glu), and phenylalanine (Phe)) as nitrogenous model compounds for biomass, and the distribution characteristics and formation mechanisms of the nitrogenous chemicals in bio-oil were studied in depth. Results showed that the amino acid structure and pyrolysis temperature were the crucial factors affecting the distribution and selectivity of nitrogenous chemicals. The nitrogenous chemicals were mainly produced at 200–500 °C from the model amino acids, and the nitrogen in Ser was more prone to accumulating in bio-oil compared with Glu and Phe. At 300 °C, the model amino acids generated numerous amines and cyclic amides through decarboxylation, decarbonylation, and dehydration. Higher temperatures (400 and 500 °C) promoted amines/amides to form nitriles and N-heterocycles, with the releasing of H2. Nitriles (including propionitrile and phenylacetonitrile) were typically produced by the straight-chain dehydrogenation of amines. Ser, Glu, and Phe produced N-heterocycles (including pyrazine, pyrrole, 2-pyrrolidone, and indole) based on the cyclization and dehydration between carbonyl and amino compounds, intramolecular dehydration, and cyclization dehydrogenation of phenethylamine, respectively. Finally, the possible formation pathways of the main nitrogenous chemicals were proposed, and the kinetics and thermodynamic analyses were performed through density functional theory (DFT) calculations. The findings could provide theoretical support for the nitrogenous chemicals production from microwave pyrolysis of amino acids and biomass.

Theoretical study on mechanism of cycloaddition reaction between o-alkynylbenzaldoximes and hexynol catalyzed by silver(I)

• A detailed description of the reaction mechanism of AgOTf-catalyzed synthesis of 2-(3-cyclopropylisoquinolin-1-yl)-1,1-diphenylhexen-3-one using DFT calculations. • Parr function analysis showed that the generation of Ag-π complexes could influence the electrophilicity of reaction species. • During intramolecular dehydration, AgOTf acts as a dehydration medium. Lewis acid metal-catalyzed cyclizations to construct quinoline ring compounds have made breakthroughs in the more recent years. Understanding the specific mechanism of this kind of reactions remains a challenging issue in this field. In this work, the mechanism of the silver(I)-catalyzed cyclization of o-alkynylbenzaldoxime with propargyl alcohol to construct 2-(3-cyclopropylisoquinolin-1-yl)-1,1-diphenylhex-1-en-3-one was investigated using density functional theory (DFT). The calculated results indicated that the 1,3-dipole cycloaddition process is the rate-determined step of the whole reaction process. The Ag-π complex formed by AgOTf with o-alkynylbenzaldehyde oxime increased the electrophilicity of the γ-C of the alkyne group prompting the intramolecular 6-endo cyclization. In addition, the Ag-π complex formed by AgOTf with alkynyl alcohol enhances the nucleophilicity of α-C atom and the electrophilicity of β-C atom of o-alkynylbenzaldehyde oxime, thus promoting the 1,3-dipole cycloaddition reaction with isoquinoline-N-oxide. The revealed mechanism will provide valuable a clue for the design of the Ag-based novel catalyst. Abstract

Impact of biomass constituent interactions on the evolution of char’s chemical structure: An organic functional group perspective

An in-depth investigation of the chemical structural evolution of char throughout the pyrolysis process is critical for subsequent biochar utilization. Therefore, the interaction mechanism among biomass constituents was studied by the examination of product distribution, bio-oil and bio-gas composition, organic functional groups, and two-dimensional correlation infrared spectrum characteristic of char. Char evolution was influenced by primary interaction (at 300 or 400 °C) and secondary interaction (at 500 or 650 °C). Polymer depolymerization and phenylpropane side chain breaking were aided by the primary interaction. Due to a “melting and wrapping” effect, it hindered ring opening, recombination, and polymerization of D-allose/D-xylose molecules, allowing the char to preserve its original C-O-C and C-OH structure. The secondary interaction stimulated the cyclization and intramolecular dehydration of D-allose, leading pyrolysis to advance to the pyran pathway. It also encouraged the ring opening, cyclization, rearrangement, and polymerization of monomer molecules, resulting in the char's C = O, C = C, and C-OH structures with greater aromatization degree. The discovery advances the understanding of the interacting mechanism of biomass pyrolysis and char formation.

A practical route to arylated dihydroacridine derivatives via nickel boride mediated intramolecular reductive cyclization-concomitant dehydration

A facile and highly efficient route towards 3-aryl-1,2-dihydroacridine derivatives from an aldol adduct of o-nitrobenzaldehyde and cyclohexenone derivatives has been described.

Pentyl valerate biofuel from γ-valerolactone in one-pot process: Insights on the key role of acid sites of the catalytic support

In this work the acid-catalysed reactions involved in the one-pot production of pentyl valerate (PV) from γ-valerolactone (GVL) and pentanol in liquid phase at 523 K, 10 bar of N 2 over acidic catalysts was studied. Two consecutive acid-catalysed reactions must be performed: (1) nucleophilic addition of pentanol (PL) to GVL to form 4-hydroxy pentyl valerate (HPV) and (2) HPV dehydration into pentyl 2-pentenoate (PP), avoiding the undesirable formation of 4-pentoxy pentyl valerate (PPV). It was found that the support activity and selectivity strongly depended on: (i) the nature; (ii) strength; (iii) density of acid sites and (iv) the textural properties of the acid support. Solids containing predominantly Lewis acid sites, such as ZnO/SiO 2 , γ-Al 2 O 3 and NaY zeolite promote mainly a strong GVL adsorption leading to a relatively high missing carbon balance. Catalysts having mainly surface Brønsted acid sites of medium–high strength, such as HPA/SiO 2 , showed a very high activity and selectivity to PP but deactivated dramatically. Zeolites containing at least 40% of Brønsted acidity and strong acid sites promoted remarkably the undesirable intramolecular dehydration of pentanol into pentenes. SiO 2 -Al 2 O 3 , exhibiting a B/(L + B) ratio of 0.21 and a wide strength of acid sites, was more selective to PP than to PPV though the missing carbon balance was high. By calorimetric adsorption and temperature-programmed oxidation adsorption enthalpies of 61.9 and 59.1 Kcal/mol for GVL and PL were obtained, respectively. Besides, by temperature-programmed desorption experiments it was determined that GVL adsorption is irreversible on SiO 2 -Al 2 O 3 , whereas in the case of PL is partially reversible. The effect of the calcination temperature on the product distribution and evolution of the missing carbon balance was also studied over SiO 2 -Al 2 O 3 . These results contribute to the future design of more efficient bifunctional catalytic systems for biofuel production.

Accelerated Dissipation of Free and Immobilized Water Facilitating the Intramolecular Dehydration of N-Xylosamine and Conversion Improvement of the Amadori Rearrangement Product of Aspartic Acid-Xylose Reaction.

Compared to the method of aqueous Maillard reaction at atmospheric pressure tandem vacuum concentration, a coupling dehydration method combining spray drying and vacuum drying was used to increase aspartic acid-xylose conversion to the Amadori rearrangement product (ARP). The water activity and moisture states were found as effective indicators to characterize the degree of dehydration of Maillard reaction intermediates and efficient formation of ARP. During the vacuum drying process, the water activity of the product powder decreased significantly. Because the formation of ARP was accompanied by intramolecular dehydration, combining spray drying and vacuum drying increased the proportion of bound water in the vacuum-dried product. Free water was easily dissipated via dehydration, which then converted the immobilized water continuously to free water, and the decreased immobilized water further converted the bound water to immobilized water. The reduction in bound water contributed to the intramolecular dehydration of N-substituted d-xylosamine, which would further be transformed to be the ARP through an intramolecular rearrangement. The yield of ARP was increased from 1.68 to 21.53% after spray drying. The ARP yield was substantially increased up to 77.9% by subsequent vacuum drying.

Investigations of prenol reactions catalyzed by zinc and molybdenum complexes

We demonstrate the formation of symmetrical and unsymmetrical allylic ethers with molybdenum catalysts for the first time. While conducting reactivity studies of biobased oxygenates as fuel blending components in the presence of molybdenum or zinc metal complexes commonly used as lubricant additives, we discovered that prenol (3-methyl-2-buten-1-ol), a promising oxygenate with good fuel properties, undergoes unexpected chemical transformations. Interestingly, its isomer, isoprenol (3-methylbut-3-en-1-ol) was unreactive towards the same metal complexes. Moreover, the results suggest that the transformations were catalytic in nature as only 1% (w/w) of lubricant molybdenum complex (Molyvan L – molybdenum di (2-ethylhexyl) phosphorodithioate) led to the almost complete consumption of prenol under certain conditions. The zinc complex (zinc dialkyldithiophosphate) also led to a rich product profile, perhaps to a lower extent than the molybdenum analog. Intrigued by these results, we fine-tuned reaction conditions (e.g., temperature, solvents, closed reactor, or reflux set-up) to maximize the conversion of prenol and generation of byproducts, enable scale-up, and subsequently separate and identify the main components found in the mixture. We determined that the most efficient reaction was neat (prenol with 1% (w/w) molybdenum catalyst) under reflux conditions and at mild temperatures (<120 °C) with 95% conversion of prenol and formation of four major products. The product profile was identified spectroscopically (nuclear magnetic resonance spectroscopy, gas chromatography via flame ionization detection, and gas chromatography-mass spectroscopy) and included isoprene, 2-methylbut-3-en-2-ol (prenol isomer alcohol), 3-methyl-3-((3-methylbut-2-en-1-y)oxy)but-1-ene (mixed alcohol ether), and 1,1′-oxybis(3-methyl-2-butene) (prenol ether). The products are consistent with the catalytic isomerization of prenol to generate a tertiary unsaturated alcohol, as well as inter and intramolecular dehydration chemistries of the two alcohols that formed ethers and isoprene, respectively. This finding is significant as it demonstrates potentially undesirable chemistries that take place when lubricants and fuels come in contact, such as the sump pump or in-cylinder. Moreover, the fuel chemistry observed in real-life scenarios may be due in part to formed by-products and not the starting oxygenate. This work highlights potential catalytic chemistries that can occur with other metal complexes commonly found in lubricants. To the best of our knowledge, this is the first demonstration of the formation of symmetrical and unsymmetrical allylic ethers with molybdenum catalysts. We propose likely mechanisms for the observed chemistries.

A new “Mitsunobu homocoupling” reaction using aldol adducts of kojic acid

In this study, we attempted to carry out the Mitsunobu 1,4-elimination using the kojic acid analog 3, which carries a hydroxymethyl group on C-6 introduced by aldol condensation, to obtain an effective Michael acceptor 4. To the ethyl acetate solution of 3 and Ph3P, diisopropyl azodicarboxylate was added quickly at 0 °C, resulting in the immediate generation of a yellow precipitate. NMR, mass spectrometry, and X-ray crystal structure analyses allowed to identify the precipitate as a diastereomeric/racemic mixture of dimeric compounds of 4. The dimerization reaction was hypothesized to occur through two major steps: (i) intramolecular dehydration of 3 by Mitsunobu reagents and (ii) homocoupling of the dehydration product 4 to form a new trans-carbon–carbon double bond. Presumably, the enol ether moiety of 4 acts as an electron donor and immediately attacks the α,β-unsaturated carbonyl group of another molecule via a reaction that can be dubbed “Mitsunobu homocoupling.”

ANALYSIS OF POLYESTERS STRUCTURE BASED ON MALIC ACID AND ITS ESTER

Four polyesters based on malic acid and its dibutyl ester were obtained. Ethylene glycol and 1,4-butanediol were used as comonomers. The reaction of polycondensation was carried out without a catalyst, and the transesterification of glycol esters was carried out in the presence of tetrobutoxytitanium in an amount of 1wt%. The malic acid during polycondensation we melted and dissolved in glycols at a temperature of 100 °C to prevent the reaction of intramolecular dehydration. The reactions were carried out for 3 hours with stirring and gradual heating of the reaction mass. The processes were carried out in a flow of nitrogen to remove the formed low-molecular products. These products were condensed and analyzed by gas-liquid chromatography. The control of the polycondensation reaction was carried out by the molecular weight determined by the viscometric method. The structure of the obtained polyesters was determined using IR and (1H, 13C) NMR spectroscopy. The obtained polymer samples represent a resinous mass from light yellow to light brown with average molecular weights from 2000 to 4000 g/mol. Analysis of IR spectra showed that in the samples obtained by ester transesterification, the intensity of the hydroxyl group band is more than that of acid and diol based polymers. This difference can be explained by the presence of polymer chain branches obtained as result of the reaction of self-condensation. Analysis of (1H, 13C) NMR spectra confirms that in the process of polycondensation of malic acid with diols, a side reaction of self-condensation of the acid occurs with the formation of branched polymer units. In the case of the use of an ester as a monomer, polyester of a linear structure is obtained. In all obtained samples of polyesters, the presence of unsaturated bonds in the structure was also observed. This confirms that a side reaction of internal malic acid dehydration took place under the synthesis conditions. To reduce the unsaturation of polyesters, the polycondensation process must be carried out at a lower temperature.

A concise synthesis of 10-benzoyl-3,4-dihydroanthracen-1(2H)-one derivatives catalyzed by TfOH under metal-free conditions

TfOH was proved to be an efficient catalyst to promote the intra-molecular cyclization, Diels-Alder reaction, deprotonation and dehydration, and provided a concise synthesis of 10-benzoyl-3,4-dihydroanthracen-1(2H)-ones in good yields from a reaction of 2-(phenylethynyl) benzaldehyde and cyclohexane-1,3-dione. It underwent in high regioselectivity when center asymmetrical 4,4-dimethylcyclohexane-1,3-dione was used as a reactant.

“Thermal-dissolution based carbon enrichment” treatment of biomass wastes: Mechanism study of biomass pyrolysis in a highly-dispersed medium

A novel treatment denoted as the “Thermal-dissolution based carbon enrichment (TDCE)” was proposed in our previous work to effectively deoxygenate and de-ash biomass under mild conditions. The main reactions during this process occurred in a highly-dispersed and inert medium, thus its mechanism was unclear. In this study, cellulose was chosen as the model compound to investigate the underlying reaction mechanisms of TDCE process. It was confirmed that three distinct stages were involved in this process, which were physical dissolution stage, intramolecular deoxygenation and rearrangement stage, and stabilization stage. The deoxygenation attributed to the intramolecular dehydration at around 300 °C and the formations of CO2 and CO through subsequent aromatization in liquid phase at around 350 °C. Around 67% and 19% of oxygen were removed by these two pathways, respectively. About 80% of carbon remained in the solid products in all conditions. A two-step process was verified for the aromatic substance formation: furan structure formation at the beginning and the subsequent conversion to benzene ring. Especially, unlike large molecular bio-char formation in conventional pyrolysis, small molecular aromatics were formed in TDCE process. Undoubtedly, the highly-dispersed and inert medium contributed to these intramolecular reactions and suppressed the intermolecular reactions, although it wasn’t involved in the chemical reactions. Hence, the unique reaction mechanism of biomass in a highly-dispersed medium was specified, providing theoretical guidance to the practical application of TDCE method.

Reformation of Thalidomide from Its Hydrolysis Compound via Intramolecular Dehydration

Thalidomide, a famous chiral drug, can be hydrolyzed into three different compounds depending on the reaction site of hydrolysis. This work presents the reformation of thalidomide from one of the hydrolysis compounds through an intramolecular dehydration reaction in acetonitrile. The difference of dehydration behavior between hydrolysis compounds was rationalized based on molecular structures: the reformable molecule has the preferable geometric environment for intramolecular dehydration.

Recent Advances on Benzofuranones: Synthesis and Transformation via C–H Functionalization

AbstractThe benzofuranone structure is important in many fields, such as natural products, pharmaceuticals, building blocks, antioxidants, and dyes. The efficient synthesis and transformation of benzofuranones have attracted great attention in organic synthesis. They can be synthesized by the Friedel–Crafts reaction and intramolecular dehydration ring-closing and transition-metal-catalyzed reactions, among others. Their direct utilization in the preparation of other functional molecules further enhance their application. Due to their low pK a value and easy enolization, the transformation of benzofuranones via C(3)–H bond functionalization has been a hot issue since 2010. Herein, we highlight advances in the synthesis of benzofuranones and their transformation via C–H functionalization. Other transformations related to benzofuranones are also discussed.1 Introduction2 Synthesis of Benzofuranones3 C–H Functionalization of Benzofuranones4 Other Types of Reactions of Benzofuranones5 Conclusion and Outlook

Oriented valorization of cellulose and xylan into anhydrosugars by using low-temperature pyrolysis

Fast pyrolysis is a promising method to convert cellulose and hemicellulose into anhydrosugars, but the current method is energy intensive and provides poor yield and selectivity for anhydrosugars. The possibility of using mineral acid pretreatment to achieve oriented pyrolysis of cellulose and xylan at low temperature was explored in this study. The pyrolysis behaviors and mechanism of cellulose and xylan were investigated by pyrolysis–gas chromatography/mass spectrometry and in-situ diffuse reflectance infrared Fourier transform spectroscopy combined with two-dimensional perturbation correlation infrared spectroscopy. The results showed that H2SO4-impregnation and HCl-demineralization achieved the oriented pyrolysis of cellulose and xylan into anhydrosugars at 300 °C. The highest yields of levoglucosan and levoglucosenone (33.3 and 9.7%) were obtained from pyrolysis of 0.1%H2SO4-impregnated cellulose at 300 °C, while those of xylosan and 1,5-anhydro-4-deoxypent-1-en-3-ulose (19.4 and 8.4%) were produced from pyrolysis of HCl-demineralized xylan at 300 °C. It is inferred that H2SO4 could promote the condensation of hydroxyls at C6 and C1 positions and the cleavage of glycosidic bonds to form levoglucosan. And AAEMs could inhibit the intra-molecular dehydration of C3 hydroxyl and C2 hydrogen atom of levoglucosan to form levoglucosenone. The demineralization of xylan could promote the cleavage of glycosidic bonds and dehydration reactions to form xylosan and 1,5-anhydro-4-deoxypent-1-en-3-ulose. These findings provide a simple method to achieve oriented pyrolysis of cellulose and xylan at low temperature.

TBAF‐Catalyzed Tandem Synthesis of Triazolo[4,5‐c]quinolines at Ambient Temperature

A mild, efficient and metal‐free synthetic method for 1H‐[1,2,3]triazolo[4,5‐c]quinolines has been developed via intermolecular [3+2] cycloaddition of β‐(2‐aminoaryl)‐α,β‐ynones and TMS‐N3, followed by intramolecular dehydration annulation sequential reactions. With 5 mmol‐% of TBAF as catalyst, the reaction can smoothly proceed in DMF at ambient temperature to afford a wide range of functionalized 1H‐[1,2,3]triazolo[4,5‐c]quinolines in good to excellent yields.