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Synergy-Promoted Specific Alkyltriphenylphosphonium Binding to CB[8]
IF 4.354 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-02-09 DOI: 10.1021/acs.joc.4c02546
Mauro Díaz-Abellás, Iago Neira, Arturo Blanco-Gómez, Carlos Peinador, Marcos D. García
Biological substrate specificity ensures that organisms interact accurately with biomolecular receptors, crucial for key functions such as signaling and immunity. Nevertheless, this phenomenon is still poorly understood, with host–guest chemistry offering a suitable platform for studying simplified models. Herein, we report an in-depth study of the host–guest chemistry of alkyltriphenylphosphonium cations with cucurbit[8]uril (CB[8]), initiated by the serendipitous discovery of salt forming a tightly bound pseudoheteroternary 1:1 complex with CB[8]. A first generation of model substrates was designed to explore an unusual binding mode characterized by the simultaneous introduction of two distinct guest fragments within the host cavity. Structural features of the complexes were elucidated using ESI-MS and NMR 1D/2D techniques; thermodynamic properties were assessed by isothermal titration calorimetry, and kinetic parameters were derived from selective inversion–recovery NMR. Experimental results aligned well with electronic structure calculations, revealing a reproducible binding motif with submicromolar affinities. This peculiar complexation mode involves a synergistic effect caused by steric crowding around the P+ atom, facilitating the insertion of two aromatic units into CB[8] while hindering association with CB[7]. Based on these findings, a second generation of minimalistic substrates was developed, preserving the synergistic interaction mode and exhibiting specific binding to CB[8].
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引用次数: 0
Electrochemically Driven Chalcogenative Cyclization of 2-Alkynyl Aryl Oxime: Access to Functionalized Isoquinolines
IF 3.3 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-02-07 DOI: 10.1021/acs.joc.4c0265510.1021/acs.joc.4c02655
Jiajun Hu, Bo Li, Feng Xiong, Yue Xu, Zheyu Li, Linghui Gu*, Wenbo Ma* and Ruhuai Mei*, 

A transition-metal-free electrochemical chalcogenative cyclization of 2-alkynyl aryl oxime with dichalcogenides has been established to assemble valuable 4-organochalcogen isoquinolines concisely. This protocol proceeds via constant electrolysis in a user-friendly undivided cell setup. It circumvents the necessity of transition metal catalysts, chemical oxidants, and harsh reaction conditions. The practical utilities of the current protocol were illustrated by excellent functional group tolerance, remarkable regio-selectivity, easy scalability, mild reaction conditions, and transformable 4-organochalcogen isoquinoline products.

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引用次数: 0
Mechanoredox-Enabled Isothiocyanation of Primary Amines Using Piezoelectric Material as the Redox Catalyst
IF 3.3 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-02-07 DOI: 10.1021/acs.joc.4c0252610.1021/acs.joc.4c02526
Miao Wang*, Hui-Ying Ren, Shan Jiang, Xiao-Yu Pu, Xiao-Lu Zhang, He-Ying Zhu, Jia-Chen Xiang* and Bang-Tun Zhao*, 

A novel mechanoredox-enabled synthesis of aromatic and aliphatic isothiocyanates from primary amines and carbon disulfide under ball milling conditions using a piezoelectric material (BaTiO3) as the redox catalyst has been developed. This method displays several features, such as short reaction time, operational simplicity, room temperature and air conditions, minimal solvent, broad substrate scope, and recyclable cheap catalyst. Preliminary mechanistic studies revealed that highly polarized piezoelectric material acted as a single-electron transfer (SET) oxidation reagent for the key desulfurization process.

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引用次数: 0
Selective Construction of 2,4-Bisthioquinolines via Copper-Catalyzed Tandem Cyclization from o-Alkynylphenyl Isothiocyanates
IF 4.354 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-02-07 DOI: 10.1021/acs.joc.4c01991
Guojian Fang, Xuan Wu, Xiaoyan Sang, Han Wang, Wenyan Hao
The selective synthesis of polysubstituted quinoline has been recognized as an important but highly challenging transformation. In this study, a highly efficient method for the synthesis of 2,4-bisthioquinolines has been developed through a copper(II)-promoted tandem cycloaddition of o-alkynylphenyl isothiocyanates, utilizing inexpensive and readily available sodium sulfide (Na2S) as the sulfur source. This transformation enables the direct synthesis of 2,4-bis(thioquinoline) heterocycles via the formation of C–C and C–S bonds in a one-pot reaction, demonstrating excellent tolerance for various functional groups.
{"title":"Selective Construction of 2,4-Bisthioquinolines via Copper-Catalyzed Tandem Cyclization from o-Alkynylphenyl Isothiocyanates","authors":"Guojian Fang, Xuan Wu, Xiaoyan Sang, Han Wang, Wenyan Hao","doi":"10.1021/acs.joc.4c01991","DOIUrl":"https://doi.org/10.1021/acs.joc.4c01991","url":null,"abstract":"The selective synthesis of polysubstituted quinoline has been recognized as an important but highly challenging transformation. In this study, a highly efficient method for the synthesis of 2,4-bisthioquinolines has been developed through a copper(II)-promoted tandem cycloaddition of <i>o</i>-alkynylphenyl isothiocyanates, utilizing inexpensive and readily available sodium sulfide (Na<sub>2</sub>S) as the sulfur source. This transformation enables the direct synthesis of 2,4-bis(thioquinoline) heterocycles via the formation of C–C and C–S bonds in a one-pot reaction, demonstrating excellent tolerance for various functional groups.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"163 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143367442","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Electrochemically Driven Chalcogenative Cyclization of 2-Alkynyl Aryl Oxime: Access to Functionalized Isoquinolines
IF 4.354 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-02-07 DOI: 10.1021/acs.joc.4c02655
Jiajun Hu, Bo Li, Feng Xiong, Yue Xu, Zheyu Li, Linghui Gu, Wenbo Ma, Ruhuai Mei
A transition-metal-free electrochemical chalcogenative cyclization of 2-alkynyl aryl oxime with dichalcogenides has been established to assemble valuable 4-organochalcogen isoquinolines concisely. This protocol proceeds via constant electrolysis in a user-friendly undivided cell setup. It circumvents the necessity of transition metal catalysts, chemical oxidants, and harsh reaction conditions. The practical utilities of the current protocol were illustrated by excellent functional group tolerance, remarkable regio-selectivity, easy scalability, mild reaction conditions, and transformable 4-organochalcogen isoquinoline products.
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引用次数: 0
Mechanoredox-Enabled Isothiocyanation of Primary Amines Using Piezoelectric Material as the Redox Catalyst
IF 4.354 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-02-07 DOI: 10.1021/acs.joc.4c02526
Miao Wang, Hui-Ying Ren, Shan Jiang, Xiao-Yu Pu, Xiao-Lu Zhang, He-Ying Zhu, Jia-Chen Xiang, Bang-Tun Zhao
A novel mechanoredox-enabled synthesis of aromatic and aliphatic isothiocyanates from primary amines and carbon disulfide under ball milling conditions using a piezoelectric material (BaTiO3) as the redox catalyst has been developed. This method displays several features, such as short reaction time, operational simplicity, room temperature and air conditions, minimal solvent, broad substrate scope, and recyclable cheap catalyst. Preliminary mechanistic studies revealed that highly polarized piezoelectric material acted as a single-electron transfer (SET) oxidation reagent for the key desulfurization process.
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引用次数: 0
Assembly of Diverse Allenes via Activator-Free Palladium-Catalyzed Regioselective γ-Arylation of Propargylamines with Boronic Acids
IF 3.3 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-02-07 DOI: 10.1021/acs.joc.4c0270810.1021/acs.joc.4c02708
Yan Sun, Ya Pan, Tao Zhao*, Junwei Li, Aiguo Gu, Junhai Huang and Huangdi Feng*, 

Controlling the reaction selectivity to achieve a precision synthesis is a constant concern for chemists. Here, we report a palladium-catalyzed deaminative coupling of propargylamines with arylboronic acids to generate allene skeletons. Importantly, this approach allows the regioselective γ-arylation of unactivated propargyl tertiary amines to access various allenes in the absence of amino-activating reagents. We present a wide range of propargylamines and boronic acids and demonstrate the synthetic application of the target products to construct valuable compounds.

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引用次数: 0
Selective Construction of 2,4-Bisthioquinolines via Copper-Catalyzed Tandem Cyclization from o-Alkynylphenyl Isothiocyanates
IF 3.3 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-02-07 DOI: 10.1021/acs.joc.4c0199110.1021/acs.joc.4c01991
Guojian Fang, Xuan Wu, Xiaoyan Sang, Han Wang and Wenyan Hao*, 

The selective synthesis of polysubstituted quinoline has been recognized as an important but highly challenging transformation. In this study, a highly efficient method for the synthesis of 2,4-bisthioquinolines has been developed through a copper(II)-promoted tandem cycloaddition of o-alkynylphenyl isothiocyanates, utilizing inexpensive and readily available sodium sulfide (Na2S) as the sulfur source. This transformation enables the direct synthesis of 2,4-bis(thioquinoline) heterocycles via the formation of C–C and C–S bonds in a one-pot reaction, demonstrating excellent tolerance for various functional groups.

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引用次数: 0
Assembly of Diverse Allenes via Activator-Free Palladium-Catalyzed Regioselective γ-Arylation of Propargylamines with Boronic Acids 通过无活化剂钯催化丙炔胺与硼酸的区域选择性γ-芳基化组装多种烯烃
IF 4.354 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-02-07 DOI: 10.1021/acs.joc.4c02708
Yan Sun, Ya Pan, Tao Zhao, Junwei Li, Aiguo Gu, Junhai Huang, Huangdi Feng
Controlling the reaction selectivity to achieve a precision synthesis is a constant concern for chemists. Here, we report a palladium-catalyzed deaminative coupling of propargylamines with arylboronic acids to generate allene skeletons. Importantly, this approach allows the regioselective γ-arylation of unactivated propargyl tertiary amines to access various allenes in the absence of amino-activating reagents. We present a wide range of propargylamines and boronic acids and demonstrate the synthetic application of the target products to construct valuable compounds.
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引用次数: 0
Cesium Carbonate-Catalyzed Oxidative Cross-Dehydrogenative Thiolation of Phosphonothioates
IF 3.3 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-02-06 DOI: 10.1021/acs.joc.4c0271810.1021/acs.joc.4c02718
Hsiu-Te Hung, Rekha Bai, Sung-Hung Lee, Indrajit Karmakar and Chin-Fa Lee*, 

Herein, we report an aerobic oxidative cross-dehydrogenative coupling (CDC) reaction between thiols and phosphonothioates. The reactions were conducted under mild and transition-metal-free conditions in the presence of air. Not only aryl thiols but also alkyl thiols were successfully coupled with phosphonothioates to form the corresponding phosphorodithioates in good to excellent yields.

{"title":"Cesium Carbonate-Catalyzed Oxidative Cross-Dehydrogenative Thiolation of Phosphonothioates","authors":"Hsiu-Te Hung,&nbsp;Rekha Bai,&nbsp;Sung-Hung Lee,&nbsp;Indrajit Karmakar and Chin-Fa Lee*,&nbsp;","doi":"10.1021/acs.joc.4c0271810.1021/acs.joc.4c02718","DOIUrl":"https://doi.org/10.1021/acs.joc.4c02718https://doi.org/10.1021/acs.joc.4c02718","url":null,"abstract":"<p >Herein, we report an aerobic oxidative <i>cross</i>-dehydrogenative coupling (CDC) reaction between thiols and phosphonothioates. The reactions were conducted under mild and transition-metal-free conditions in the presence of air. Not only aryl thiols but also alkyl thiols were successfully coupled with phosphonothioates to form the corresponding phosphorodithioates in good to excellent yields.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 6","pages":"2534–2541 2534–2541"},"PeriodicalIF":3.3,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.joc.4c02718","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143402369","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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Journal of Organic Chemistry
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