Pub Date : 2026-04-21Epub Date: 2026-02-21DOI: 10.1039/d6qo00093b
Lu Pei , Xiao-Lin Liu , Ding-Jun Zhang , Hui-Hong Tian , Ling-Dan Zhu , Bang-Guo Wei
A Pd(PPh3)4-catalyzed regioselective C–H para-allylation process was developed for the reaction of N,N-dialkylanilines with vinyl benzoxazinanones. Such transformation demonstrated a novel application of vinyl benzoxazinanone reagents, allowing for the introduction of an alkenyl group exclusively into the para-position of aniline derivatives. As a result, a series of N,N-dialkylaniline derivatives with para-allyl type substituents were synthesized with excellent regioselectivities (E : Z ratios >19 : 1).
{"title":"Pd(PPh3)4-catalyzed regioselective C–H para-allylation of N,N-dialkylanilines using vinyl benzoxazinanones","authors":"Lu Pei , Xiao-Lin Liu , Ding-Jun Zhang , Hui-Hong Tian , Ling-Dan Zhu , Bang-Guo Wei","doi":"10.1039/d6qo00093b","DOIUrl":"10.1039/d6qo00093b","url":null,"abstract":"<div><div>A Pd(PPh<sub>3</sub>)<sub>4</sub>-catalyzed regioselective C–H <em>para</em>-allylation process was developed for the reaction of <em>N</em>,<em>N</em>-dialkylanilines with vinyl benzoxazinanones. Such transformation demonstrated a novel application of vinyl benzoxazinanone reagents, allowing for the introduction of an alkenyl group exclusively into the <em>para</em>-position of aniline derivatives. As a result, a series of <em>N</em>,<em>N</em>-dialkylaniline derivatives with <em>para</em>-allyl type substituents were synthesized with excellent regioselectivities (<em>E</em> : <em>Z</em> ratios >19 : 1).</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 8","pages":"Pages 2417-2423"},"PeriodicalIF":0.0,"publicationDate":"2026-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146231044","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-04-21Epub Date: 2026-02-26DOI: 10.1039/d5qo01752a
Guo Cheng , Jing-Liang Yu , Qian-Mao Zhang , Zhen-Yu Yang , Fang Tian , Li-Xin Wang
A highly enantioselective oxidative homocoupling of naphthylboronic acids/boronates has been reported for the first time using an easily available chiral P,N-ligand/PdCl2 partner only under an oxygen atmosphere. A series of axially chiral binaphthyls have been prepared in excellent enantioselectivities (92% ee to 99% ee) in all cases with acceptable yields (up to 73% yield). This protocol complements the Suzuki and Chan–Lam couplings. This enantioselective homocoupling is enabled by the discovery of the first air(oxygen)-stable chiral P,N palladium complex capable of functioning even at high temperatures – conditions that are incompatible with most existing chiral phosphine ligands. These findings could aid the design and screening of new air-stable, temperature-tolerant chiral phosphine complexes and expand their application in catalytic redox reactions.
{"title":"An air-stable chiral P,N-ligand/PdCl2 partner enables a highly enantioselective oxidative homocoupling of naphthylboronic acids/boronates only in an oxygen atmosphere","authors":"Guo Cheng , Jing-Liang Yu , Qian-Mao Zhang , Zhen-Yu Yang , Fang Tian , Li-Xin Wang","doi":"10.1039/d5qo01752a","DOIUrl":"10.1039/d5qo01752a","url":null,"abstract":"<div><div>A highly enantioselective oxidative homocoupling of naphthylboronic acids/boronates has been reported for the first time using an easily available chiral P,N-ligand/PdCl<sub>2</sub> partner only under an oxygen atmosphere. A series of axially chiral binaphthyls have been prepared in excellent enantioselectivities (92% ee to 99% ee) in all cases with acceptable yields (up to 73% yield). This protocol complements the Suzuki and Chan–Lam couplings. This enantioselective homocoupling is enabled by the discovery of the first air(oxygen)-stable chiral P,N palladium complex capable of functioning even at high temperatures – conditions that are incompatible with most existing chiral phosphine ligands. These findings could aid the design and screening of new air-stable, temperature-tolerant chiral phosphine complexes and expand their application in catalytic redox reactions.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 8","pages":"Pages 2410-2416"},"PeriodicalIF":0.0,"publicationDate":"2026-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147320186","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A rhenium-catalyzed, highly efficient, regio- and stereoselective hydrocarboxylation of internal alkynes and olefins has been developed. This simple, atom- and step-economic strategy provides facile access to functionalized aryl enol esters in high yields. Notably, several NSAID drug molecules (e.g., oxaprozin, ibuprofen, indomethacin, ketoprofen, naproxen, flurbiprofen, etc.) underwent hydrocarboxylation without the need for pre-functionalization. Deuterium-labeling studies revealed that proton transfer originates from the COOH group, while O–H bond cleavage is unlikely to be involved in the turnover-determining transition state (TDTS) of the catalytic cycle.
{"title":"Rhenium-catalyzed stereoselective hydrocarboxylation of alkynes and olefins: late-stage NSAID drug's diversification","authors":"Suman Bhowmick , Mayank Singh , Khushboo Tiwari , Dharmendra Kumar Tiwari","doi":"10.1039/d5qo01612f","DOIUrl":"10.1039/d5qo01612f","url":null,"abstract":"<div><div>A rhenium-catalyzed, highly efficient, regio- and stereoselective hydrocarboxylation of internal alkynes and olefins has been developed. This simple, atom- and step-economic strategy provides facile access to functionalized aryl enol esters in high yields. Notably, several NSAID drug molecules (<em>e.g.</em>, oxaprozin, ibuprofen, indomethacin, ketoprofen, naproxen, flurbiprofen, <em>etc.</em>) underwent hydrocarboxylation without the need for pre-functionalization. Deuterium-labeling studies revealed that proton transfer originates from the COOH group, while O–H bond cleavage is unlikely to be involved in the turnover-determining transition state (TDTS) of the catalytic cycle.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 8","pages":"Pages 2316-2322"},"PeriodicalIF":0.0,"publicationDate":"2026-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146223001","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-04-21Epub Date: 2026-02-11DOI: 10.1039/d5qo01741f
Albert Artigas , Nicolas Vanthuyne , Jean-Valère Naubron , Denis Hagebaum-Reignier , Yannick Carissan , Maxime Rémond , Ludovic Favereau , Harald Bock , Fabien Durola , Yoann Coquerel
The in-depth analysis of the configurational, (chir)optical and aromatic properties of two diastereomeric singly and triply twisted Möbius-shaped macrocycles, the cyclotris[5]helicenes, in which three [5]helicene fragments with like and unlike helicity are connected by three C(sp2)–C(sp2) single bonds, led to the conclusion that global π electronic delocalization exists in these molecules. This was analyzed as a consequence of the reduced torsion angle (≤30°) at the C(sp2)–C(sp2) single bonds connecting the [5]helicene fragments. The enantiomers of both diastereomeric cyclotris[5]helicenes were thoroughly analyzed experimentally by unpolarized and circularly polarized vibrational, absorption and luminescence (fluorescence and phosphorescence) spectroscopies, all correlated with advanced DFT models, which provided insightful data on their S0, S1 and T1 electronic states, and on their chirality. The theoretical analyses of aromaticity in both diastereomeric cyclotris[5]helicene macrocycles, as compared with recently reported analogues, confirmed their Möbius aromaticity.
{"title":"Electronic properties of diastereomeric Möbius shaped cyclotris[5]helicenes","authors":"Albert Artigas , Nicolas Vanthuyne , Jean-Valère Naubron , Denis Hagebaum-Reignier , Yannick Carissan , Maxime Rémond , Ludovic Favereau , Harald Bock , Fabien Durola , Yoann Coquerel","doi":"10.1039/d5qo01741f","DOIUrl":"10.1039/d5qo01741f","url":null,"abstract":"<div><div>The in-depth analysis of the configurational, (chir)optical and aromatic properties of two diastereomeric singly and triply twisted Möbius-shaped macrocycles, the cyclotris[5]helicenes, in which three [5]helicene fragments with <em>like</em> and <em>unlike</em> helicity are connected by three C(sp<sup>2</sup>)–C(sp<sup>2</sup>) single bonds, led to the conclusion that global π electronic delocalization exists in these molecules. This was analyzed as a consequence of the reduced torsion angle (≤30°) at the C(sp<sup>2</sup>)–C(sp<sup>2</sup>) single bonds connecting the [5]helicene fragments. The enantiomers of both diastereomeric cyclotris[5]helicenes were thoroughly analyzed experimentally by unpolarized and circularly polarized vibrational, absorption and luminescence (fluorescence and phosphorescence) spectroscopies, all correlated with advanced DFT models, which provided insightful data on their S<sub>0</sub>, S<sub>1</sub> and T<sub>1</sub> electronic states, and on their chirality. The theoretical analyses of aromaticity in both diastereomeric cyclotris[5]helicene macrocycles, as compared with recently reported analogues, confirmed their Möbius aromaticity.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 8","pages":"Pages 2298-2308"},"PeriodicalIF":0.0,"publicationDate":"2026-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146160910","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Herein, using tricarbazole as an electron donor and four aromatic rings with various electron cloud densities as acceptors, four homologous donor–acceptor (D–A) architectures () were divergently synthesized and characterized. Their steady-state and transient photophysical properties were subsequently investigated, in which their intramolecular charge transfer transitions were disclosed by solvent-dependent fluorescence spectra. Interestingly, an electron-rich acceptor could result in a blue shift in fluorescence, while an electron-deficient acceptor led to red-shifted fluorescence emission. Furthermore, intense and stable electrochemiluminescence (ECL) signals were observed for all architectures. In contrast, the ECL intensity was enhanced with increasing electron cloud density of the acceptor. Finally, , displaying optimal ECL performance, was used as an electrode modification material to construct an epinephrine sensor, which demonstrated high sensitivity, excellent stability, and remarkable selectivity. This work elucidated the regulatory role of the electron cloud density of the acceptor on the optoelectronic properties of D–A architectures and provides new insights for developing novel high-performance optoelectronic materials and sensors.
{"title":"Tricarbazole-based donor–acceptor architectures with diverse acceptors: synthesis, properties and applications","authors":"Huabi Xie , Yu Zuo , Chengye Yuan , Peng Xu , Ningwen Sun , Hongxing Jia , Jinjin Ding , Qiang Huang , Jinling Zhang","doi":"10.1039/d5qo01633a","DOIUrl":"10.1039/d5qo01633a","url":null,"abstract":"<div><div>Herein, using tricarbazole as an electron donor and four aromatic rings with various electron cloud densities as acceptors, four homologous donor–acceptor (D–A) architectures () were divergently synthesized and characterized. Their steady-state and transient photophysical properties were subsequently investigated, in which their intramolecular charge transfer transitions were disclosed by solvent-dependent fluorescence spectra. Interestingly, an electron-rich acceptor could result in a blue shift in fluorescence, while an electron-deficient acceptor led to red-shifted fluorescence emission. Furthermore, intense and stable electrochemiluminescence (ECL) signals were observed for all architectures. In contrast, the ECL intensity was enhanced with increasing electron cloud density of the acceptor. Finally, , displaying optimal ECL performance, was used as an electrode modification material to construct an epinephrine sensor, which demonstrated high sensitivity, excellent stability, and remarkable selectivity. This work elucidated the regulatory role of the electron cloud density of the acceptor on the optoelectronic properties of D–A architectures and provides new insights for developing novel high-performance optoelectronic materials and sensors.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 8","pages":"Pages 2382-2387"},"PeriodicalIF":0.0,"publicationDate":"2026-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146184559","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-04-21Epub Date: 2026-02-21DOI: 10.1039/d6qo00008h
Kanak Kanti Das , Sutapa Dey
Boryl-substituted cyclobutanes have emerged as valuable building blocks that merge the structural rigidity and strain-enabled reactivity of four-membered rings with the versatile synthetic utility of organoboron chemistry. Here, the recent advances in the synthesis of boryl-substituted cyclobutanes, a class of strained, sp3-rich building blocks that combine the structural rigidity of cyclobutanes with the exceptional versatility of organoboron chemistry, have been summarized. Emphasis is placed on strategies that exploit boronate complex reactivity and 1,2-migration processes to overcome the inherent challenges associated with four-membered ring formation. Thermal, photochemical, and transition-metal-catalysed approaches are discussed, highlighting how strain-release, radical polar crossover, and σ-bond activation enable efficient and stereocontrolled cyclobutane construction. Key mechanistic insights that govern selectivity and reactivity also have been outlined across diverse platforms.
{"title":"Advances in the construction of boryl cyclobutanes","authors":"Kanak Kanti Das , Sutapa Dey","doi":"10.1039/d6qo00008h","DOIUrl":"10.1039/d6qo00008h","url":null,"abstract":"<div><div>Boryl-substituted cyclobutanes have emerged as valuable building blocks that merge the structural rigidity and strain-enabled reactivity of four-membered rings with the versatile synthetic utility of organoboron chemistry. Here, the recent advances in the synthesis of boryl-substituted cyclobutanes, a class of strained, sp<sup>3</sup>-rich building blocks that combine the structural rigidity of cyclobutanes with the exceptional versatility of organoboron chemistry, have been summarized. Emphasis is placed on strategies that exploit boronate complex reactivity and 1,2-migration processes to overcome the inherent challenges associated with four-membered ring formation. Thermal, photochemical, and transition-metal-catalysed approaches are discussed, highlighting how strain-release, radical polar crossover, and σ-bond activation enable efficient and stereocontrolled cyclobutane construction. Key mechanistic insights that govern selectivity and reactivity also have been outlined across diverse platforms.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 8","pages":"Pages 2641-2656"},"PeriodicalIF":0.0,"publicationDate":"2026-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146231042","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-04-21Epub Date: 2026-02-17DOI: 10.1039/d5qo01692d
Xiao-Yi Deng , Yun-Zhe Li , Zhong Xie , Wen-Run Zhu , Yi Liu , Gui Lu , Jiang Weng
A chiral phosphoric acid-catalyzed asymmetric mono- and double-allenylation of carbazoles with α-indolyl propargylic alcohols was realized. This highly efficient protocol produces diverse chiral tetrasubstituted allenes in excellent yields with remarkable chemo-, regio- and enantioselectivities under mild conditions. The practicality of this efficient method is further demonstrated by the good anticancer activities of the obtained chiral allenylationalized carbazole derivatives.
{"title":"Asymmetric C3-allenylation of carbazoles with α-indolyl propargylic alcohols","authors":"Xiao-Yi Deng , Yun-Zhe Li , Zhong Xie , Wen-Run Zhu , Yi Liu , Gui Lu , Jiang Weng","doi":"10.1039/d5qo01692d","DOIUrl":"10.1039/d5qo01692d","url":null,"abstract":"<div><div>A chiral phosphoric acid-catalyzed asymmetric mono- and double-allenylation of carbazoles with α-indolyl propargylic alcohols was realized. This highly efficient protocol produces diverse chiral tetrasubstituted allenes in excellent yields with remarkable chemo-, regio- and enantioselectivities under mild conditions. The practicality of this efficient method is further demonstrated by the good anticancer activities of the obtained chiral allenylationalized carbazole derivatives.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 8","pages":"Pages 2352-2359"},"PeriodicalIF":0.0,"publicationDate":"2026-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146210446","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-04-21Epub Date: 2026-02-23DOI: 10.1039/d5qo01757b
Xiao-Xia You , Ling-Qi Meng , Xu Liu , Li-Li Wang , Xin-Cheng Xu , Rong-Lin Zhong , Zhong-Min Su
This study employs density functional theory (DFT) calculations to elucidate the mechanism and alkali metal-dependent reactivity in the Ni0-catalyzed C(sp2)–F bond activation of fluoronaphthalenes, assisted by lithium acetylides. The results reveal that the energy barrier for C(sp2)–F bond activation initiated by the acetylide carbanion is 30.1 kcal mol−1, significantly higher than that (18.5 kcal mol−1) for the ethide carbanion-initiated one, due to the notably weaker nucleophilicity of the acetylide carbanion. Interestingly, the reaction between lithium acetylides and the pre-catalyst Ni0(cod)2 generates a Ni0(acetylide carbanion)-ate complex, in which high nucleophilicity is localized at the Ni0-center. Significantly, the energy barrier for C(sp2)–F bond activation catalyzed by the Ni0(acetylide carbanion)-ate complex via an inner-sphere nucleophilic aromatic substitution (SNAr) pathway is considerably lowered to 25.3 kcal mol−1. Theoretical analysis clarifies that the distinct reactivity of the ate complex stems from coordination of the acetylide carbanion to the Ni0 center, with strong Li⋯F interactions serving as a key driving force to stabilize the transition state. This work provides a comprehensive insight into transition metal-catalyzed C–F bond activation with the assistance of an acetylide carbanion, which is expected to offer a theoretical perspective for the rational design of C–F functionalization strategies.
{"title":"Theoretical investigation on the mechanism of Ni0(acetylide carbanion)-ate complex-catalyzed C(sp2)–F bond activation and the origin of the counterion effect on reactivity","authors":"Xiao-Xia You , Ling-Qi Meng , Xu Liu , Li-Li Wang , Xin-Cheng Xu , Rong-Lin Zhong , Zhong-Min Su","doi":"10.1039/d5qo01757b","DOIUrl":"10.1039/d5qo01757b","url":null,"abstract":"<div><div>This study employs density functional theory (DFT) calculations to elucidate the mechanism and alkali metal-dependent reactivity in the Ni<sup>0</sup>-catalyzed C(sp<sup>2</sup>)–F bond activation of fluoronaphthalenes, assisted by lithium acetylides. The results reveal that the energy barrier for C(sp<sup>2</sup>)–F bond activation initiated by the acetylide carbanion is 30.1 kcal mol<sup>−1</sup>, significantly higher than that (18.5 kcal mol<sup>−1</sup>) for the ethide carbanion-initiated one, due to the notably weaker nucleophilicity of the acetylide carbanion. Interestingly, the reaction between lithium acetylides and the pre-catalyst Ni<sup>0</sup>(cod)<sub>2</sub> generates a Ni<sup>0</sup>(acetylide carbanion)-ate complex, in which high nucleophilicity is localized at the Ni<sup>0</sup>-center. Significantly, the energy barrier for C(sp<sup>2</sup>)–F bond activation catalyzed by the Ni<sup>0</sup>(acetylide carbanion)-ate complex <em>via</em> an inner-sphere nucleophilic aromatic substitution (S<sub>N</sub>Ar) pathway is considerably lowered to 25.3 kcal mol<sup>−1</sup>. Theoretical analysis clarifies that the distinct reactivity of the ate complex stems from coordination of the acetylide carbanion to the Ni<sup>0</sup> center, with strong Li⋯F interactions serving as a key driving force to stabilize the transition state. This work provides a comprehensive insight into transition metal-catalyzed C–F bond activation with the assistance of an acetylide carbanion, which is expected to offer a theoretical perspective for the rational design of C–F functionalization strategies.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 8","pages":"Pages 2341-2351"},"PeriodicalIF":0.0,"publicationDate":"2026-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147279960","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-04-21Epub Date: 2026-02-20DOI: 10.1039/d5qo01765c
Shengchen Wei , Yingjie Peng , Dan Shi , Xiangzhao Zhu , Songhua Chen , Lili Xie , Yuanming Li
This work presents the first modular synthesis method for acepleiadylene derivatives which were synthesized through Suzuki coupling of biphenyl compounds with acenaphthenylboronic acid followed by 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) oxidation. Through the control of functional blocks, the manipulation of the structure of acepleiadylene derivatives was achieved, which in turn led to different photoelectric properties. Modification and π-extension of APD were accomplished at the 5, 6, 7, and 8 positions. A comprehensive investigation of their structural, photophysical, and electronic properties was performed through experiments and theoretical calculations.
{"title":"A modular approach toward 5,6,7,8-functionalized acepleiadylene derivatives","authors":"Shengchen Wei , Yingjie Peng , Dan Shi , Xiangzhao Zhu , Songhua Chen , Lili Xie , Yuanming Li","doi":"10.1039/d5qo01765c","DOIUrl":"10.1039/d5qo01765c","url":null,"abstract":"<div><div>This work presents the first modular synthesis method for acepleiadylene derivatives which were synthesized through Suzuki coupling of biphenyl compounds with acenaphthenylboronic acid followed by 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) oxidation. Through the control of functional blocks, the manipulation of the structure of acepleiadylene derivatives was achieved, which in turn led to different photoelectric properties. Modification and π-extension of APD were accomplished at the 5, 6, 7, and 8 positions. A comprehensive investigation of their structural, photophysical, and electronic properties was performed through experiments and theoretical calculations.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 8","pages":"Pages 2444-2449"},"PeriodicalIF":0.0,"publicationDate":"2026-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146231189","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-04-21Epub Date: 2026-02-28DOI: 10.1039/d6qo00075d
Han-Jiang Yang , Yatuan Ma , Xinpei Zhong , Xin Yang , You Xu , Xiaoxue Zhang , Zhixin Xiang , Xiujuan Huang , Wenji Wang , Jinyi Wang , Mao-Sen Yuan
The exploration of Z/E stereoisomers represents an interesting and significant endeavor in molecular engineering. We developed three pairs of tetraphenylethylene (TPE) derivatives modified with heteroatom-containing trivalent arylboron and/or tris(2-methylpyridyl)amine (TPA) to explore differences in the optical properties, morphologies, and sensing applications between the Z and E stereoisomers. These isomers exhibit similar photophysical properties in the solution state and obvious differences in the amorphous aggregate and crystal states. All E-isomers exhibit tighter molecular packing and spatial interactions compared with the Z-isomers, resulting in longer-wavelength fluorescence emission. For the first time, TPE-based Z/E-isomers were separated by using a strategy in which different crystals emit different fluorescence under ultraviolet lamps. The single-crystal X-ray structures reveal the molecular configurations and luminescence mechanisms, allowing for a discussion on the pattern of the through-space charge transfer. The ultramarine fluorescence emission of the Z-isomer () should originate from the staggered molecular pairs, and the green fluorescence of the E-isomer () should originate from J-type molecular aggregations. In addition, the E isomer () shows a highly selective and sensitive response to HPO42− based on the restriction of intramolecular rotation-induced fluorescence enhancement of TPE and the synergistic coordination effect of triarylboron and metal ions chelated by TPA. This work extends the family of stereoisomers available in molecular engineering with new structures and correlated morphologies and functionalities and demonstrates the design, separation, and evaluation of the Z and E stereoisomers of TPE and their derivatives.
{"title":"Engineering tetraphenylethene-based Z and E stereoisomers: structural analysis and sensing applications","authors":"Han-Jiang Yang , Yatuan Ma , Xinpei Zhong , Xin Yang , You Xu , Xiaoxue Zhang , Zhixin Xiang , Xiujuan Huang , Wenji Wang , Jinyi Wang , Mao-Sen Yuan","doi":"10.1039/d6qo00075d","DOIUrl":"10.1039/d6qo00075d","url":null,"abstract":"<div><div>The exploration of <em>Z</em>/<em>E</em> stereoisomers represents an interesting and significant endeavor in molecular engineering. We developed three pairs of tetraphenylethylene (TPE) derivatives modified with heteroatom-containing trivalent arylboron and/or tris(2-methylpyridyl)amine (TPA) to explore differences in the optical properties, morphologies, and sensing applications between the <em>Z</em> and <em>E</em> stereoisomers. These isomers exhibit similar photophysical properties in the solution state and obvious differences in the amorphous aggregate and crystal states. All <em>E</em>-isomers exhibit tighter molecular packing and spatial interactions compared with the <em>Z</em>-isomers, resulting in longer-wavelength fluorescence emission. For the first time, TPE-based <em>Z</em>/<em>E</em>-isomers were separated by using a strategy in which different crystals emit different fluorescence under ultraviolet lamps. The single-crystal X-ray structures reveal the molecular configurations and luminescence mechanisms, allowing for a discussion on the pattern of the through-space charge transfer. The ultramarine fluorescence emission of the <em>Z</em>-isomer () should originate from the staggered molecular pairs, and the green fluorescence of the <em>E</em>-isomer () should originate from J-type molecular aggregations. In addition, the <em>E</em> isomer () shows a highly selective and sensitive response to HPO<sub>4</sub><sup>2−</sup> based on the restriction of intramolecular rotation-induced fluorescence enhancement of TPE and the synergistic coordination effect of triarylboron and metal ions chelated by TPA. This work extends the family of stereoisomers available in molecular engineering with new structures and correlated morphologies and functionalities and demonstrates the design, separation, and evaluation of the <em>Z</em> and <em>E</em> stereoisomers of TPE and their derivatives.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 8","pages":"Pages 2479-2486"},"PeriodicalIF":0.0,"publicationDate":"2026-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147330085","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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