A highly efficient cascade aza‐MIRC (Michael Induced Ring Closure) reaction between trifluoromethylpyrazole (TFPZ)‐derived oxadienes and a‐bromohydroxamates has been developed for the construction of 1,4‐oxazepinone derivatives. The reaction proceeds smoothly under mild conditions via a cascade Aza‐Michael addition/intramolecular SN2 sequence, and features broad substrate scope, transition‐metal free, operational simplicity etc. The utility of the versatile protocol was also demonstrated by gram‐scale reaction and valuable synthetic transformations.
{"title":"Construction of 1,4‐Oxazepinones via a Cascade Aza‐Michael/SN2 Annulation of Trifluoromethyl Pyrazole‐Derived Oxadienes with a‐Bromohydroxamates","authors":"","doi":"10.1002/ajoc.202400244","DOIUrl":"10.1002/ajoc.202400244","url":null,"abstract":"<div><div>A highly efficient cascade aza‐MIRC (Michael Induced Ring Closure) reaction between trifluoromethylpyrazole (TFPZ)‐derived oxadienes and <em>a</em>‐bromohydroxamates has been developed for the construction of 1,4‐oxazepinone derivatives. The reaction proceeds smoothly under mild conditions <em>via</em> a cascade Aza‐Michael addition/intramolecular S<sub>N</sub>2 sequence, and features broad substrate scope, transition‐metal free, operational simplicity etc. The utility of the versatile protocol was also demonstrated by gram‐scale reaction and valuable synthetic transformations.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 10","pages":"Article e202400244"},"PeriodicalIF":2.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141547856","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Enantioenriched 2‐substituted piperidines are very important unit for drug discovery. Ready access to a wide range of such compounds, decorated with functional handles at 2‐position with stereo‐defined centre significantly enhance the quality and diversity of chemical libraries for screening of drug discovery. The ability to control the stereochemistry of piperidine at the 2‐position remains an area of interest in organic synthesis to allow the development of novel, structurally diverse 3D molecules. Among the various ways to obtain enantioenriched 2‐substituted piperidines, asymmetric hydrogenation is widely studied. Asymmetric synthesis, Kinetic resolution, and chiral pool synthesis methodologies are also important ways to obtain the enantioenriched 2‐substituted piperidines. This review article summarized the main four ways to achieve particularly the enantioenriched substituted piperidines only at 2‐position considering the chemical routes, excluding the biocatalytic approach. 1. Introduction 2.1 Asymmetric Hydrogenation of 2‐substituted Pyridines 2.2 Asymmetric Synthesis 2.3. Kinetic resolution of racemic 2‐substituted Piperidine derivatives 2.4. Chiral pool synthesis 3. Conclusions & outlook
{"title":"Recent Advances in Synthesis of Enantioenriched 2‐Substituted Piperidine Derivatives","authors":"","doi":"10.1002/ajoc.202400257","DOIUrl":"10.1002/ajoc.202400257","url":null,"abstract":"<div><div>Enantioenriched 2‐substituted piperidines are very important unit for drug discovery. Ready access to a wide range of such compounds, decorated with functional handles at 2‐position with stereo‐defined centre significantly enhance the quality and diversity of chemical libraries for screening of drug discovery. The ability to control the stereochemistry of piperidine at the 2‐position remains an area of interest in organic synthesis to allow the development of novel, structurally diverse 3D molecules. Among the various ways to obtain enantioenriched 2‐substituted piperidines, asymmetric hydrogenation is widely studied. Asymmetric synthesis, Kinetic resolution, and chiral pool synthesis methodologies are also important ways to obtain the enantioenriched 2‐substituted piperidines. This review article summarized the main four ways to achieve particularly the enantioenriched substituted piperidines only at 2‐position considering the chemical routes, excluding the biocatalytic approach. 1. Introduction 2.1 Asymmetric Hydrogenation of 2‐substituted Pyridines 2.2 Asymmetric Synthesis 2.3. Kinetic resolution of racemic 2‐substituted Piperidine derivatives 2.4. Chiral pool synthesis 3. Conclusions & outlook</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 10","pages":"Article e202400257"},"PeriodicalIF":2.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141547859","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Chromenes and 2H‐Chromenes are vital components of natural products, pharmaceuticals, and agrochemicals that have captured the attention of researchers worldwide. These heterocyclic compounds represent an essential class of structural scaffolds, and the quest for their synthesis in a mild and straightforward way has gained significant momentum. Chromenes are oxygen‐containing heterocycles that have been widely studied due to their potential medicinal properties. In the last two decades, researchers have made remarkable progress towards the synthesis of chromene based heterocyclic compounds using O‐propargylated benzaldehydes as a substrate. These substrates are highly versatile and contain functional groups that make them ideal for a wide range of reactions. This review article provides an in‐depth analysis of the latest advances in alkynes’ functionalization, emphasizing the substrate scope, limitations, regioselectivity control, and applications of these reactions. The review also covers a range of critical methods and strategies, including multicomponent reactions, used for the general synthesis of numerous types of chromene derivatives.
{"title":"Recent Advances on Synthesis of 2H‐Chromenes, and Chromenes Fused Hetrocyclic Compounds","authors":"Rohit Kumar Maurya , Ashutosh Dey , Vikash Kumara , Mahender Khatravath","doi":"10.1002/ajoc.202400259","DOIUrl":"10.1002/ajoc.202400259","url":null,"abstract":"<div><div>Chromenes and <em>2H</em>‐Chromenes are vital components of natural products, pharmaceuticals, and agrochemicals that have captured the attention of researchers worldwide. These heterocyclic compounds represent an essential class of structural scaffolds, and the quest for their synthesis in a mild and straightforward way has gained significant momentum. Chromenes are oxygen‐containing heterocycles that have been widely studied due to their potential medicinal properties. In the last two decades, researchers have made remarkable progress towards the synthesis of chromene based heterocyclic compounds using O‐propargylated benzaldehydes as a substrate. These substrates are highly versatile and contain functional groups that make them ideal for a wide range of reactions. This review article provides an in‐depth analysis of the latest advances in alkynes’ functionalization, emphasizing the substrate scope, limitations, regioselectivity control, and applications of these reactions. The review also covers a range of critical methods and strategies, including multicomponent reactions, used for the general synthesis of numerous types of chromene derivatives.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 10","pages":"Article e202400259"},"PeriodicalIF":2.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141609397","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Imidazo[1,2‐c]quinazoline, a class of fused imidazole and quinazoline acceptor units, is widely established as biologically and broadly spectral active materials, while their optoelectronic properties were seldom investigated in the literature. In this context, this research work introduced two donors of varying strength, such as triphenylamine (TP) and phenothiazine (PZ) units, into the phenanthroimidazo [1,2‐c] quinazoline acceptor unit to form donor‐acceptor type luminescence materials such as TPQZ and PZQZ, respectively and were characterized by NMR and mass spectroscopy. Both these materials exhibited intramolecular charge transfer (ICT) type absorption (∼380–450 nm) and emission (∼540–600 nm) characteristics, which attributed to the electronic transition occurring from the HOMO of the TP/PZ donor to the LUMO+1 and LUMO+2 of the imidazo [1,2‐c] quinazoline acceptor unit, as predicted using DFT calculations. Increasing the electron donor strength was not only limited to fine‐tuning the π→π* based localized (∼400–450 nm) to ICT (∼450–650 nm) emission characteristics in both the solution and solid‐state conditions but also found to improve the zone of inhibition to 16 mm against Staphylococcus aureus/Bacillus subtilis bacterial species. The scope of realizing the luminescence nature of this acceptor unit is further expanded towards tagging biological samples such as E. coli. Overall, this work opens up a new paradigm in developing luminescent materials utilizing imidazo[1,2‐c]quinazoline acceptor unit for optoelectronic and biological applications.
{"title":"Unravelling the Optoelectronic and Biological Properties of Phenanthroimidazo [1,2‐c] Quinazoline‐Based Donor‐Acceptor Materials","authors":"Prabhu Ganesan , Revathi Ranganathan , Rajadurai Vijay Solomon , Peer Muhamed Noorani , Paramaguru Ganesan , Nooruddin Thajuddin , Anbazhagan Venkattappan , Renganathan Rajalingam , Peng Gao","doi":"10.1002/ajoc.202400285","DOIUrl":"10.1002/ajoc.202400285","url":null,"abstract":"<div><div>Imidazo[1,2‐c]quinazoline, a class of fused imidazole and quinazoline acceptor units, is widely established as biologically and broadly spectral active materials, while their optoelectronic properties were seldom investigated in the literature. In this context, this research work introduced two donors of varying strength, such as triphenylamine (TP) and phenothiazine (PZ) units, into the phenanthroimidazo [1,2‐c] quinazoline acceptor unit to form donor‐acceptor type luminescence materials such as TPQZ and PZQZ, respectively and were characterized by NMR and mass spectroscopy. Both these materials exhibited intramolecular charge transfer (ICT) type absorption (∼380–450 nm) and emission (∼540–600 nm) characteristics, which attributed to the electronic transition occurring from the HOMO of the TP/PZ donor to the LUMO+1 and LUMO+2 of the imidazo [1,2‐c] quinazoline acceptor unit, as predicted using DFT calculations. Increasing the electron donor strength was not only limited to fine‐tuning the π→π* based localized (∼400–450 nm) to ICT (∼450–650 nm) emission characteristics in both the solution and solid‐state conditions but also found to improve the zone of inhibition to 16 mm against <em>Staphylococcus aureus</em>/<em>Bacillus subtilis</em> bacterial species. The scope of realizing the luminescence nature of this acceptor unit is further expanded towards tagging biological samples such as E. coli. Overall, this work opens up a new paradigm in developing luminescent materials utilizing imidazo[1,2‐c]quinazoline acceptor unit for optoelectronic and biological applications.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 10","pages":"Article e202400285"},"PeriodicalIF":2.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141649636","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
We demonstrated that the combination of a Pd(0) catalyst and a water‐soluble TPPMS ligand has high activity for the direct arylation of readily available allylic alcohols in the Tsuji–Trost type cross‐coupling. Various organoboron reagents can be applied, enabling rapid access to the corresponding arylated products with a wide range of functional group tolerance. Kinetic studies revealed a first‐order rate dependence for the allylic alcohol, boronic acid, CsF and Pd(0)/TPPMS concentrations. A Hammett study found a slightly positive ρ value of 0.79, suggesting that a partial negative charge is generated on the aromatic ring of the aryl boronate in the rate‐determining transmetalation step. Based on several control experiments, we concluded that the transmetalation employing CsF would proceed via the oxo‐palladium mechanism.
{"title":"Pd(0)/TPPMS‐Catalyzed Tsuji–Trost Type Cross‐Coupling of Allylic Alcohols with Organoboron Compounds in Water","authors":"","doi":"10.1002/ajoc.202400132","DOIUrl":"10.1002/ajoc.202400132","url":null,"abstract":"<div><div>We demonstrated that the combination of a Pd(0) catalyst and a water‐soluble TPPMS ligand has high activity for the direct arylation of readily available allylic alcohols in the Tsuji–Trost type cross‐coupling. Various organoboron reagents can be applied, enabling rapid access to the corresponding arylated products with a wide range of functional group tolerance. Kinetic studies revealed a first‐order rate dependence for the allylic alcohol, boronic acid, CsF and Pd(0)/TPPMS concentrations. A Hammett study found a slightly positive <em>ρ</em> value of 0.79, suggesting that a partial negative charge is generated on the aromatic ring of the aryl boronate in the rate‐determining transmetalation step. Based on several control experiments, we concluded that the transmetalation employing CsF would proceed <em>via</em> the oxo‐palladium mechanism.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 10","pages":"Article e202400132"},"PeriodicalIF":2.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141520290","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
An improved synthetic procedure for the intramolecular ketene [2+2] cycloaddition was developed for the preparation of 1‐heteroatom‐substituted bicyclo[2.1.1]hexan‐5‐ones. It was found that the use of the Mukaiyama reagent (2‐chloro‐N‐methyl‐pyridinium iodide) was key to efficiently generate the α‐heteroatom substituted homoallyl ketene intermediate for the cycloaddition reaction. The synthetic utility of the resulting bicyclic ketone was demonstrated through the preparation of a saturated variant of vortioxetine.
{"title":"Intramolecular [2+2] Cycloadditions of α‐Heteroatom Substituted γ,δ‐Unsaturated Ketenes","authors":"","doi":"10.1002/ajoc.202400302","DOIUrl":"10.1002/ajoc.202400302","url":null,"abstract":"<div><div>An improved synthetic procedure for the intramolecular ketene [2+2] cycloaddition was developed for the preparation of 1‐heteroatom‐substituted bicyclo[2.1.1]hexan‐5‐ones. It was found that the use of the Mukaiyama reagent (2‐chloro‐<em>N</em>‐methyl‐pyridinium iodide) was key to efficiently generate the α‐heteroatom substituted homoallyl ketene intermediate for the cycloaddition reaction. The synthetic utility of the resulting bicyclic ketone was demonstrated through the preparation of a saturated variant of vortioxetine.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 10","pages":"Article e202400302"},"PeriodicalIF":2.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141520293","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Furanocoumarins are attractive targets in the synthetic organic and medicinal chemistry field because of their structural diversity and interesting biological properties. Herein, we describe the synthesis of furanocoumarin natural products from common furanocoumarin skeletons. A key step was a novel intramolecular radical cyclization onto nitrile to synthesize angular and linear franocoumarins, which was optimized by reacting iodocoumarin derivatives in the presence of (Me3Si)3SiH and oxygen. These compounds served as intermediates in the syntheses of vaginidiol, vaginidin, oroselol, multivittan D, gaudichaudine, oreoselone, peucedanin, and smyrindiol, successfully demonstrating the versatility of the intermediates and utility of the radical cyclization method for accessing furanocoumarin natural products.
{"title":"Collective Synthesis of Furanocoumarin Natural Products Through a Radical‐mediated Construction of Furanocoumarin Skeletons","authors":"Yuko Kotaka , Masaya Nakajima , Tetsuhiro Nemoto","doi":"10.1002/ajoc.202400277","DOIUrl":"10.1002/ajoc.202400277","url":null,"abstract":"<div><div>Furanocoumarins are attractive targets in the synthetic organic and medicinal chemistry field because of their structural diversity and interesting biological properties. Herein, we describe the synthesis of furanocoumarin natural products from common furanocoumarin skeletons. A key step was a novel intramolecular radical cyclization onto nitrile to synthesize angular and linear franocoumarins, which was optimized by reacting iodocoumarin derivatives in the presence of (Me<sub>3</sub>Si)<sub>3</sub>SiH and oxygen. These compounds served as intermediates in the syntheses of vaginidiol, vaginidin, oroselol, multivittan D, gaudichaudine, oreoselone, peucedanin, and smyrindiol, successfully demonstrating the versatility of the intermediates and utility of the radical cyclization method for accessing furanocoumarin natural products.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 10","pages":"Article e202400277"},"PeriodicalIF":2.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141614394","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Fused polycyclic aromatic compounds containing carbazole and diazapyrene skeletons as electron donors and acceptors, respectively, were synthesized in a few steps from readily accessible starting materials. The incorporation of diazapyrene units into the polycyclic compounds resulted in significant bathochromic shifts in their absorption and emission bands compared to those of the corresponding carbazole derivatives. Electrochemical measurements and density functional theory calculations were performed to gain further insight into their electronic properties. Our findings demonstrate that the incorporation of nitrogen atoms and substituents, as well as the different topologies of the fused‐ring system, exert a profound effect on the electronic properties of the polycyclic compounds.
{"title":"Synthesis and Properties of Fused Polycyclic Donor–Acceptor Compounds Containing Carbazole and Diazapyrene Skeletons","authors":"Suzuho Kurimoto , Yoshimitsu Tachi , Masatoshi Kozaki","doi":"10.1002/ajoc.202400289","DOIUrl":"10.1002/ajoc.202400289","url":null,"abstract":"<div><div>Fused polycyclic aromatic compounds containing carbazole and diazapyrene skeletons as electron donors and acceptors, respectively, were synthesized in a few steps from readily accessible starting materials. The incorporation of diazapyrene units into the polycyclic compounds resulted in significant bathochromic shifts in their absorption and emission bands compared to those of the corresponding carbazole derivatives. Electrochemical measurements and density functional theory calculations were performed to gain further insight into their electronic properties. Our findings demonstrate that the incorporation of nitrogen atoms and substituents, as well as the different topologies of the fused‐ring system, exert a profound effect on the electronic properties of the polycyclic compounds.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 10","pages":"Article e202400289"},"PeriodicalIF":2.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141739997","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The contamination of water by organic dye compounds are worldwide environmental problem due to their highly toxic nature. To address this environmental issue, a simple technique with highly efficient dye removal was developed to prepare pH‐ sensitive dual‐crosslinked anionic and amphoteric interpenetrating network (IPN) hydrogels based on Na‐carboxymethyl cellulose (Na‐CMC) using jute stick‐based cellulose. Crosslinked Na‐CMC and crosslinked κ‐carrageenan (KC) were interlaced by H‐bonding in anionic IPN hydrogel (An‐gel), but crosslinked Na‐CMC and crosslinked Chitosan (CS) were interlaced by electrostatic interaction in amphoteric IPN hydrogel (Am‐gel). In various operating conditions (pH, temperature, etc.) An‐gel displayed a higher number of swelling ratios of about 2560% at pH 7.2 and Am‐gel of about 1874% at pH 5.5. Based on the point of zero charge, An‐gel achieved the maximum removal efficiency of 81.62 % for methylene blue (MB) at pH 7.2, whereas Am‐gel achieved 85.38% removal efficiency for eosin yellow (EY) at pH 5.5. The adsorption kinetics of IPN hydrogels followed a pseudo‐second order model and best fitted by Langmuir isotherm model. The removal efficiency of MB and EY decreased slightly with increasing temperature. The values of ΔH°, ΔG°, and ΔS° indicated an exothermic, spontaneous, and disordered adsorption process.
{"title":"pH Sensitive Dual Cross‐Linked Anionic and Amphoteric Interpenetrating Network Hydrogels for Adsorptive Removal of Anionic and Cationic Dyes","authors":"","doi":"10.1002/ajoc.202400238","DOIUrl":"10.1002/ajoc.202400238","url":null,"abstract":"<div><div>The contamination of water by organic dye compounds are worldwide environmental problem due to their highly toxic nature. To address this environmental issue, a simple technique with highly efficient dye removal was developed to prepare pH‐ sensitive dual‐crosslinked anionic and amphoteric interpenetrating network (IPN) hydrogels based on Na‐carboxymethyl cellulose (Na‐CMC) using jute stick‐based cellulose. Crosslinked Na‐CMC and crosslinked κ‐carrageenan (KC) were interlaced by H‐bonding in anionic IPN hydrogel (An‐gel), but crosslinked Na‐CMC and crosslinked Chitosan (CS) were interlaced by electrostatic interaction in amphoteric IPN hydrogel (Am‐gel). In various operating conditions (pH, temperature, etc.) An‐gel displayed a higher number of swelling ratios of about 2560% at pH 7.2 and Am‐gel of about 1874% at pH 5.5. Based on the point of zero charge, An‐gel achieved the maximum removal efficiency of 81.62 % for methylene blue (MB) at pH 7.2, whereas Am‐gel achieved 85.38% removal efficiency for eosin yellow (EY) at pH 5.5. The adsorption kinetics of IPN hydrogels followed a pseudo‐second order model and best fitted by Langmuir isotherm model. The removal efficiency of MB and EY decreased slightly with increasing temperature. The values of ΔH°, ΔG°, and ΔS° indicated an exothermic, spontaneous, and disordered adsorption process.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 10","pages":"Article e202400238"},"PeriodicalIF":2.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141520292","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A novel bismuth(III) trifluoro‐methanesulfonate‐catalyzed and environmentally benign synthetic strategy for the construction of a wide range of structurally diverse, sophisticated [5,6,5]‐oxygen‐containing tricyclic frameworks with easy‐to handle propargylic alcohols and 2‐allylphenols as substrates in the presence of Bi(OTf)3 and AgOTf is described. This Lewis acid catalyzed [3+2] annulation protocol, which tolerates a great deal of functional groups, proceeds through a sequential Meyer‐Schuster rearrangement, nucleophilic substitution, 5‐exo‐trig cyclization, 5‐endo‐trig cyclization, and proton exchange sequences, affording a versatile approach for accessing oxygen‐containing tricyclic skeletons in moderate‐to‐excellent yields. In addition, most of the obtained compounds exhibited anti‐tumor activities against three types of human cancer cell lines in vitro, including Caco‐2 colon cancer cells, MCF‐7 breast cancer cells, and Hepg‐2 liver cancer cells.
{"title":"Lewis Acid‐Catalyzed Tandem Annulation of Propargylic Alcohols with 2‐Allylphenols and Their Anti‐tumor Activities","authors":"","doi":"10.1002/ajoc.202400265","DOIUrl":"10.1002/ajoc.202400265","url":null,"abstract":"<div><div>A novel bismuth(III) trifluoro‐methanesulfonate‐catalyzed and environmentally benign synthetic strategy for the construction of a wide range of structurally diverse, sophisticated [5,6,5]‐oxygen‐containing tricyclic frameworks with easy‐to handle propargylic alcohols and 2‐allylphenols as substrates in the presence of Bi(OTf)<sub>3</sub> and AgOTf is described. This Lewis acid catalyzed [3+2] annulation protocol, which tolerates a great deal of functional groups, proceeds through a sequential Meyer‐Schuster rearrangement, nucleophilic substitution, 5‐<em>exo</em>‐trig cyclization, 5‐<em>endo</em>‐trig cyclization, and proton exchange sequences, affording a versatile approach for accessing oxygen‐containing tricyclic skeletons in moderate‐to‐excellent yields. In addition, most of the obtained compounds exhibited anti‐tumor activities against three types of human cancer cell lines <em>in vitro</em>, including Caco‐2 colon cancer cells, MCF‐7 breast cancer cells, and Hepg‐2 liver cancer cells.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 10","pages":"Article e202400265"},"PeriodicalIF":2.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141547852","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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