Man Zhong , Xin‐Yue Li , Jin Zhang , Li Chen , Yun‐Long Hu , Yang Li
The selective functionalization of difluoromethyl groups (−CF2) is a promising approach and an attractive synthetic route for accessing fluorine‐containing moieties with medicinal benefits. Here, we report a case of a C−N coupling reaction between bromodifluoropropene with heterocyclic amines, such as indole, pyrrole, and imidazole, promoted by an alkali without the use of transition metal catalysis. This reaction differs from existing methods in that it does not undergo a difluoromethylation isomerization reaction but directly retains the structure of the terminal olefin. This chemical conversion process has a wide substrate range, good functional group tolerance, and an ideal reaction conversion rate, making it an effective new method for the difluoropropenation of heterocyclic amines.
{"title":"Promotion of Metal‐Free Catalytic Coupling of Fluorinated Halogenated Hydrocarbons By a Base for the Synthesis of Difluoromethyl Heterocyclic Amines","authors":"Man Zhong , Xin‐Yue Li , Jin Zhang , Li Chen , Yun‐Long Hu , Yang Li","doi":"10.1002/ajoc.202400541","DOIUrl":"10.1002/ajoc.202400541","url":null,"abstract":"<div><div>The selective functionalization of difluoromethyl groups (−CF<sub>2</sub>) is a promising approach and an attractive synthetic route for accessing fluorine‐containing moieties with medicinal benefits. Here, we report a case of a C−N coupling reaction between bromodifluoropropene with heterocyclic amines, such as indole, pyrrole, and imidazole, promoted by an alkali without the use of transition metal catalysis. This reaction differs from existing methods in that it does not undergo a difluoromethylation isomerization reaction but directly retains the structure of the terminal olefin. This chemical conversion process has a wide substrate range, good functional group tolerance, and an ideal reaction conversion rate, making it an effective new method for the difluoropropenation of heterocyclic amines.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 2","pages":"Article e202400541"},"PeriodicalIF":2.8,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143424247","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}
Weijian Ye , Aoyun Lu , Ziyi Zhang , Guodan Lu , Xiangshuai Du , Prof. Dr. Yong Wang , Prof. Dr. Xiaobing Wan
Self‐assembly with non‐covalent interactions (NCIs) is a ubiquitous phenomenon observed in biology and materials chemistry, while its application in synthetic chemistry is still in its infancy. Herein, a self‐assembly condensation method from sulfonamides and imides is reported, leading to the formation of N‐acyl‐N′‐sulfonyl amidines. DFT calculations and NMR investigations suggest that the process is facilitated by cooperative assisted NCIs, including hydrogen bonding and Lewis pairs. Moreover, this methodology can be applied in the late‐stage derivatization of bioactive and complex sulfonamides, offering a potential avenue for the discovery of drug molecules. Extension of this methodology to the condensation of various sulfonamides and amides has also been successfully achieved.
{"title":"Construction of N‐Sulfonyl Amidines: Self‐Assembly through Synergy between Hydrogen Bonding and Lewis Pairs","authors":"Weijian Ye , Aoyun Lu , Ziyi Zhang , Guodan Lu , Xiangshuai Du , Prof. Dr. Yong Wang , Prof. Dr. Xiaobing Wan","doi":"10.1002/ajoc.202400600","DOIUrl":"10.1002/ajoc.202400600","url":null,"abstract":"<div><div>Self‐assembly with non‐covalent interactions (NCIs) is a ubiquitous phenomenon observed in biology and materials chemistry, while its application in synthetic chemistry is still in its infancy. Herein, a self‐assembly condensation method from sulfonamides and imides is reported, leading to the formation of <em>N</em>‐acyl‐<em>N</em>′‐sulfonyl amidines. DFT calculations and NMR investigations suggest that the process is facilitated by cooperative assisted NCIs, including hydrogen bonding and Lewis pairs. Moreover, this methodology can be applied in the late‐stage derivatization of bioactive and complex sulfonamides, offering a potential avenue for the discovery of drug molecules. Extension of this methodology to the condensation of various sulfonamides and amides has also been successfully achieved.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 2","pages":"Article e202400600"},"PeriodicalIF":2.8,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143423716","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}
Min‐Ji Kim , Gwiung Nam , Soyoon Lee , Mina Ahn , Prof. Dae Won Cho , Prof. Kyung‐Ryang Wee
Organic luminescent materials have garnered significant attention owing to their potential applications, particularly due to their inherent flexibility and ease of processability. Accordingly, the development of strategies that enable precise control over both intra‐ and intermolecular interactions, which directly influence their emission properties, is of paramount importance. In this study, a series of naphthalene (NAP) 2,7‐position‐based donor–acceptor–donor (D−A−D) compounds were designed and synthesized to investigate the electron push‐pull effect on intramolecular and intermolecular interactions. The energy bandgaps of the compounds were controlled by the electron push‐pull effect, resulting in red‐shifted emission within 48 nm in the order of increasing electron‐donating ability in solution state. Experimental data and theoretical calculations show that the intramolecular charge transfer (ICT) properties of D−A−D compounds are systematically controlled by electron push‐pull effects. In particular, the solid‐state emission of the compounds showed a redshift in the same order as that observed in solution. This solid‐state emission behavior is explained by the electron push‐pull effect‐dependent intermolecular interactions. Consequently, an efficient single‐molecule and multi‐molecule emission control strategy by electron push‐pull effect in NAP 2,7‐position‐based D−A−D was successfully demonstrated.
{"title":"Electron Push‐Pull Effects for Solution and Solid‐State Emission Control in Naphthalene 2,7‐Position‐Based Donor–Acceptor–Donor","authors":"Min‐Ji Kim , Gwiung Nam , Soyoon Lee , Mina Ahn , Prof. Dae Won Cho , Prof. Kyung‐Ryang Wee","doi":"10.1002/ajoc.202400631","DOIUrl":"10.1002/ajoc.202400631","url":null,"abstract":"<div><div>Organic luminescent materials have garnered significant attention owing to their potential applications, particularly due to their inherent flexibility and ease of processability. Accordingly, the development of strategies that enable precise control over both intra‐ and intermolecular interactions, which directly influence their emission properties, is of paramount importance. In this study, a series of naphthalene (NAP) 2,7‐position‐based donor–acceptor–donor (D−A−D) compounds were designed and synthesized to investigate the electron push‐pull effect on intramolecular and intermolecular interactions. The energy bandgaps of the compounds were controlled by the electron push‐pull effect, resulting in red‐shifted emission within 48 nm in the order of increasing electron‐donating ability in solution state. Experimental data and theoretical calculations show that the intramolecular charge transfer (ICT) properties of D−A−D compounds are systematically controlled by electron push‐pull effects. In particular, the solid‐state emission of the compounds showed a redshift in the same order as that observed in solution. This solid‐state emission behavior is explained by the electron push‐pull effect‐dependent intermolecular interactions. Consequently, an efficient single‐molecule and multi‐molecule emission control strategy by electron push‐pull effect in NAP 2,7‐position‐based D−A−D was successfully demonstrated.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 2","pages":"Article e202400631"},"PeriodicalIF":2.8,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143423874","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}
Luyao Dai , Guangwei Shao , Xiaoxiao You , Li Chen , Di Wu , Jianlong Xia
Terrylene diimides (TDIs), as the higher homologues of perylene diimide (PDI) in the series of rylene diimides (RDIs), exhibit several especial properties including enhanced absorption ability in the near infrared (NIR) region, higher fluorescence quantum yields as well as stronger π–π stacking in comparison to naphthalene diimides (NDIs) and perylene diimides (PDIs). However, TDIs have been largely overlooked in terms of their photovoltaic applications because of the chemical inaccessibility and poor solubility. In this contribution, a helical π‐extended terrylene diimide dimer based on ring‐fused ethylene bridge, namely FTDI2 is designed and synthesized. The photovoltaic performances of FTDI2 and the parent TDI are investigated using the commercially available PTB7‐Th as the electron donor. A significantly improved power‐conversion efficiency (PCE) of 5.11 % compared to that of TDI based ones (0.5 %) is achieved for FTDI2‐based device, demonstrating the potential of terrylene dyes in the photovoltaics field.
{"title":"Helical π‐Extended Terrylene Diimide Dimer Based on Ring‐Fused Ethylene Bridge for Organic Solar Cells","authors":"Luyao Dai , Guangwei Shao , Xiaoxiao You , Li Chen , Di Wu , Jianlong Xia","doi":"10.1002/ajoc.202400548","DOIUrl":"10.1002/ajoc.202400548","url":null,"abstract":"<div><div>Terrylene diimides (TDIs), as the higher homologues of perylene diimide (PDI) in the series of rylene diimides (RDIs), exhibit several especial properties including enhanced absorption ability in the near infrared (NIR) region, higher fluorescence quantum yields as well as stronger π–π stacking in comparison to naphthalene diimides (NDIs) and perylene diimides (PDIs). However, TDIs have been largely overlooked in terms of their photovoltaic applications because of the chemical inaccessibility and poor solubility. In this contribution, a helical π‐extended terrylene diimide dimer based on ring‐fused ethylene bridge, namely <strong>FTDI2</strong> is designed and synthesized. The photovoltaic performances of <strong>FTDI2</strong> and the parent TDI are investigated using the commercially available PTB7‐Th as the electron donor. A significantly improved power‐conversion efficiency (PCE) of 5.11 % compared to that of TDI based ones (0.5 %) is achieved for <strong>FTDI2</strong>‐based device, demonstrating the potential of terrylene dyes in the photovoltaics field.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 2","pages":"Article e202400548"},"PeriodicalIF":2.8,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143424123","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 concise and metal‐free procedure has been developed for the synthesis of 2‐vinylanilines. Reactions of indolines with tert‐BuOK in DMSO afford the decorated 2‐vinylanilines in yields up to 92 %. In addition, the 2, or 3‐substituted indolines could be converted to trisubstituted alkenes. Also, the protocol can be scaled to afford gram quantities of the decorated 2‐vinylanilines.
{"title":"Potassium tert‐Butoxide‐Mediated Ring‐Opening of Indolines: Concise Synthesis of 2‐Vinylanilines","authors":"Keisuke Tokushige , Shota Asai , Takumi Abe","doi":"10.1002/ajoc.202400552","DOIUrl":"10.1002/ajoc.202400552","url":null,"abstract":"<div><div>A concise and metal‐free procedure has been developed for the synthesis of 2‐vinylanilines. Reactions of indolines with <em>tert</em>‐BuOK in DMSO afford the decorated 2‐vinylanilines in yields up to 92 %. In addition, the 2, or 3‐substituted indolines could be converted to trisubstituted alkenes. Also, the protocol can be scaled to afford gram quantities of the decorated 2‐vinylanilines.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 2","pages":"Article e202400552"},"PeriodicalIF":2.8,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143424121","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}
Zhongwenqin Lian , Xin Ge , Hejun Chen , Mukerimu Wusiman , Keyume Ablajan
A NaI‐promoted efficient synthesis of 2‐aryl benzothiazoles/benzoxazoles with various substituted acyl chlorides is described. The reaction proceeded using more environment‐friendly H2O media as a solvent. Mechanism studies verified that the reaction undergoes a ring‐opening process. This novel method could be suitable for benzothiazole and benzoxazole to afford good yields of arylated products. This protocol has the potential for further application due to its broad substrate scopes.
{"title":"NaI‐promoted Synthesis of 2‐aryl Benzothiazole/Benzoxazole in Aqueous Medium","authors":"Zhongwenqin Lian , Xin Ge , Hejun Chen , Mukerimu Wusiman , Keyume Ablajan","doi":"10.1002/ajoc.202400497","DOIUrl":"10.1002/ajoc.202400497","url":null,"abstract":"<div><div>A NaI‐promoted efficient synthesis of 2‐aryl benzothiazoles/benzoxazoles with various substituted acyl chlorides is described. The reaction proceeded using more environment‐friendly H<sub>2</sub>O media as a solvent. Mechanism studies verified that the reaction undergoes a ring‐opening process. This novel method could be suitable for benzothiazole and benzoxazole to afford good yields of arylated products. This protocol has the potential for further application due to its broad substrate scopes.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 2","pages":"Article e202400497"},"PeriodicalIF":2.8,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143424255","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}
Haruna Sugimura , Kana Nakajima , Ken‐ichi Yamashita
Isophlorins, which are two‐electron reduced porphyrins, have garnered significant interest because of their potential antiaromaticity and unique electronic properties. However, the isolation of stable antiaromatic isophlorins remains challenging because they are prone to oxidation or reduction to the corresponding aromatic molecules, or are structurally distorted, resulting in loss of antiaromaticity. Here, we report the synthesis and characterization of a Sn(IV) β‐tetracyanoisophlorin complex obtained through two‐electron reduction of the corresponding Sn(IV) β‐tetracyanoporphyrin complex. This Sn(IV) complex exhibits enhanced antiaromaticity owing to its highly planar structure, facilitated by the central Sn atom. X‐ray crystal diffraction analysis revealed that the Sn(IV) isophlorin complex contains two methoxy groups as axial ligands and that it exists as a divalent anion, demonstrating the oxophilic nature of the Sn(IV) isophlorin complexes. Notably, this Sn(IV) isophlorin complex is stable under air, distinguishing it from previously reported Si(IV) and Ge(IV) isophlorin complexes without cyano groups. This study thus presents the first isolation of an air‐stable metal complex of antiaromatic isophlorin, opening new possibilities for exploring the unique properties of antiaromatic porphyrinoids for various applications, including catalysis and materials science.
{"title":"Synthesis and Characterization of an Air‐Stable Tin(IV) β‐Tetracyanoisophlorin Complex: Enhanced Antiaromaticity through Metal Complexation.","authors":"Haruna Sugimura , Kana Nakajima , Ken‐ichi Yamashita","doi":"10.1002/ajoc.202400550","DOIUrl":"10.1002/ajoc.202400550","url":null,"abstract":"<div><div>Isophlorins, which are two‐electron reduced porphyrins, have garnered significant interest because of their potential antiaromaticity and unique electronic properties. However, the isolation of stable antiaromatic isophlorins remains challenging because they are prone to oxidation or reduction to the corresponding aromatic molecules, or are structurally distorted, resulting in loss of antiaromaticity. Here, we report the synthesis and characterization of a Sn(IV) β‐tetracyanoisophlorin complex obtained through two‐electron reduction of the corresponding Sn(IV) β‐tetracyanoporphyrin complex. This Sn(IV) complex exhibits enhanced antiaromaticity owing to its highly planar structure, facilitated by the central Sn atom. X‐ray crystal diffraction analysis revealed that the Sn(IV) isophlorin complex contains two methoxy groups as axial ligands and that it exists as a divalent anion, demonstrating the oxophilic nature of the Sn(IV) isophlorin complexes. Notably, this Sn(IV) isophlorin complex is stable under air, distinguishing it from previously reported Si(IV) and Ge(IV) isophlorin complexes without cyano groups. This study thus presents the first isolation of an air‐stable metal complex of antiaromatic isophlorin, opening new possibilities for exploring the unique properties of antiaromatic porphyrinoids for various applications, including catalysis and materials science.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 2","pages":"Article e202400550"},"PeriodicalIF":2.8,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ajoc.202400550","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143424310","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Zhoubin Deng , Yuyu Lv , Ke‐Hu Wang , Danfeng Huang , Junjiao Wang , Yulai Hu
Various N‐methacryloyl‐2‐arylbenzoimidazoles react with 1,2‐dibromotetrafluoroethane in the presence of photocatalyst 4CzIPN irradiated by 10 W blue LED to provide 5‐(3‐bromo‐2,2,3,3‐tetrafluoropropyl)‐5‐methylbenzo[4,5]‐imidazo[2,1‐a]isoquinolin‐6(5H)‐ones in good yield. The reaction proceeds through a sequential tetrafluoroethyl radical addition/cyclization pathway. The wide substrate scope, good functional group tolerance, and ease of scale‐up of this protocol are expected to promote its potential applications in pharmacy.
{"title":"Light‐Induced Tetrafluoroethylation/Cyclization of N‐Methacryloyl‐2‐phenylbenzoimidazoles with 1,2‐Dibromotetrafluoroethane","authors":"Zhoubin Deng , Yuyu Lv , Ke‐Hu Wang , Danfeng Huang , Junjiao Wang , Yulai Hu","doi":"10.1002/ajoc.202400620","DOIUrl":"10.1002/ajoc.202400620","url":null,"abstract":"<div><div>Various <em>N</em>‐methacryloyl‐2‐arylbenzoimidazoles react with 1,2‐dibromotetrafluoroethane in the presence of photocatalyst 4CzIPN irradiated by 10 W blue LED to provide 5‐(3‐bromo‐2,2,3,3‐tetrafluoropropyl)‐5‐methylbenzo[4,5]‐imidazo[2,1‐a]isoquinolin‐6(5<em>H</em>)‐ones in good yield. The reaction proceeds through a sequential tetrafluoroethyl radical addition/cyclization pathway. The wide substrate scope, good functional group tolerance, and ease of scale‐up of this protocol are expected to promote its potential applications in pharmacy.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 2","pages":"Article e202400620"},"PeriodicalIF":2.8,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143424314","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}
This paper proposes a molecular design for open‐shell singlet biradicals through a synthetic study of phospholo[3,4‐c]thiophenes in which the phosphole ring is fused with thiophene. The sulfur‐bridged diyne was converted into the titanacycle intermediate, and the subsequent treatment with chlorodiphenylphosphine provided the corresponding phosphole via the [2+2+1] cycloaddition process. The −CH2SCH2‐bridged phosphole oxide could be isomerized to the corresponding thiophene structure probably because of the larger aromaticity of thiophene rather than phosphole. The 4,6‐dihydrophospholo[3,4‐c]thiophene 5‐oxide derivative was triflated to give the thiophene‐fused cyclic phosphonium salt, which could generate the desired singlet biradical by treatment with potassium hydride. In addition, pai‐extension of the 4,6‐dihydrophospholo[3,4‐c]thiophene 5‐oxide unit using the Pd‐catalyzed cross‐coupling reaction with arylstannanes was accomplished, and the resultant isolable 5,6‐dihydro‐4H‐phospholo[3,4‐c]thiophene derivatives showed potent characters as precursors of singlet biradical. The generation of biradical phospholo[3,4‐c]thiophenes was supported by the [4+2] trapping reaction and the 1,2‐migration leading to a cyclic phosphaalkene.
{"title":"A Synthetic Approach to Singlet Phospholo[3,4‐c]thiophene Biradicals via the Conversion from Phosphole to Thiophene","authors":"Yasuhiro Ueta , Junnosuke Kasai , Shigekazu Ito","doi":"10.1002/ajoc.202400616","DOIUrl":"10.1002/ajoc.202400616","url":null,"abstract":"<div><div>This paper proposes a molecular design for open‐shell singlet biradicals through a synthetic study of phospholo[3,4‐<em>c</em>]thiophenes in which the phosphole ring is fused with thiophene. The sulfur‐bridged diyne was converted into the titanacycle intermediate, and the subsequent treatment with chlorodiphenylphosphine provided the corresponding phosphole via the [2+2+1] cycloaddition process. The −CH<sub>2</sub>SCH<sub>2</sub>‐bridged phosphole oxide could be isomerized to the corresponding thiophene structure probably because of the larger aromaticity of thiophene rather than phosphole. The 4,6‐dihydrophospholo[3,4‐<em>c</em>]thiophene 5‐oxide derivative was triflated to give the thiophene‐fused cyclic phosphonium salt, which could generate the desired singlet biradical by treatment with potassium hydride. In addition, pai‐extension of the 4,6‐dihydrophospholo[3,4‐<em>c</em>]thiophene 5‐oxide unit using the Pd‐catalyzed cross‐coupling reaction with arylstannanes was accomplished, and the resultant isolable 5,6‐dihydro‐4<em>H</em>‐phospholo[3,4‐<em>c</em>]thiophene derivatives showed potent characters as precursors of singlet biradical. The generation of biradical phospholo[3,4‐<em>c</em>]thiophenes was supported by the [4+2] trapping reaction and the 1,2‐migration leading to a cyclic phosphaalkene.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 2","pages":"Article e202400616"},"PeriodicalIF":2.8,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ajoc.202400616","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143424311","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Zhimin Sang , Zijin Luo , Jingao Chen , Wenxue Gou , Guofu Zhang , Chengrong Ding
The trifluoromethylthio group (−SCF3) exhibits several distinctive physicochemical properties and can alter the molecular lipophilicity and other pharmacokinetic properties of functional molecules. Moreover, its potent electron‐withdrawing capability confers enhanced metabolic stability to functional molecules. Molecules containing trifluoromethylthio groups are extensively applied in the synthesis of pharmaceuticals or agrochemicals and have garnered significant attention in recent years. The synthetic routes to trifluoromethylthio groups primarily fall into two categories: direct introduction of −SCF3 into target molecules, and indirect construction of −SCF3 through the introduction of −CF3 into sulfur‐containing precursors. In this review, we delineate approaches developed over the past seven years for the indirect construction of −SCF3 groups via electrophilic, nucleophilic, radical, or other types of reactions involving −CF3 groups and sulfur‐containing precursors. These reactions are classified into seven categories depending on the employed: thiols, disulfides, thiosulfates, sodium sulfinates, sulfonyl chlorides, sulfoxides, and other sulfur‐containing precursors.
{"title":"Synthesis of Trifluoromethylthio Compounds from Sulfur‐Containing Precursors","authors":"Zhimin Sang , Zijin Luo , Jingao Chen , Wenxue Gou , Guofu Zhang , Chengrong Ding","doi":"10.1002/ajoc.202400588","DOIUrl":"10.1002/ajoc.202400588","url":null,"abstract":"<div><div>The trifluoromethylthio group (−SCF<sub>3</sub>) exhibits several distinctive physicochemical properties and can alter the molecular lipophilicity and other pharmacokinetic properties of functional molecules. Moreover, its potent electron‐withdrawing capability confers enhanced metabolic stability to functional molecules. Molecules containing trifluoromethylthio groups are extensively applied in the synthesis of pharmaceuticals or agrochemicals and have garnered significant attention in recent years. The synthetic routes to trifluoromethylthio groups primarily fall into two categories: direct introduction of −SCF<sub>3</sub> into target molecules, and indirect construction of −SCF<sub>3</sub> through the introduction of −CF<sub>3</sub> into sulfur‐containing precursors. In this review, we delineate approaches developed over the past seven years for the indirect construction of −SCF<sub>3</sub> groups via electrophilic, nucleophilic, radical, or other types of reactions involving −CF<sub>3</sub> groups and sulfur‐containing precursors. These reactions are classified into seven categories depending on the employed: thiols, disulfides, thiosulfates, sodium sulfinates, sulfonyl chlorides, sulfoxides, and other sulfur‐containing precursors.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 2","pages":"Article e202400588"},"PeriodicalIF":2.8,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143423717","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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