Long-Jin Zhong, Xuan Shang, Pengfei Huang, Quan Zhou, Changhui Liu, Yu Liu
We report a study on the use of ligated boryl radicals for the synthesis of nitrogen-containing polycyclic compounds under photocatalytic conditions through a halogen-atom transfer (XAT) strategy. This approach leverages the fact that alkyl iodides are not capable of directly generating alkyl radical intermediates under photocatalytic conditions. Instead, the transformation proceeds via a XAT pathway involving boron-centered radical intermediates. A range of alkyl halogen (1°, 2° and 3° C-I, C-Br) as well as alkyl iodides derivatives of biologically active molecules (Such as Ibuprofen, Citronellol, Geraniol, Cholesterol, Estrone et. al.) are applicable in the strategy. Finally, a scale-up synthesis and late-stage modification in Sonogashira cross-coupling reactions of structurally complex molecules demonstrate the practicability of this methodology.
{"title":"Halogen Atom Transfer-Induced Radical Cascades Cyclization of N-(o-Cyanobiaryl)acrylamides with Alkyl Halides via Boryl Radical-Mediated","authors":"Long-Jin Zhong, Xuan Shang, Pengfei Huang, Quan Zhou, Changhui Liu, Yu Liu","doi":"10.1039/d5qo01481f","DOIUrl":"https://doi.org/10.1039/d5qo01481f","url":null,"abstract":"We report a study on the use of ligated boryl radicals for the synthesis of nitrogen-containing polycyclic compounds under photocatalytic conditions through a halogen-atom transfer (XAT) strategy. This approach leverages the fact that alkyl iodides are not capable of directly generating alkyl radical intermediates under photocatalytic conditions. Instead, the transformation proceeds via a XAT pathway involving boron-centered radical intermediates. A range of alkyl halogen (1°, 2° and 3° C-I, C-Br) as well as alkyl iodides derivatives of biologically active molecules (Such as Ibuprofen, Citronellol, Geraniol, Cholesterol, Estrone et. al.) are applicable in the strategy. Finally, a scale-up synthesis and late-stage modification in Sonogashira cross-coupling reactions of structurally complex molecules demonstrate the practicability of this methodology.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"31 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147330263","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Easily available trialkylamines are increasingly utilized as coupling partners with diverse hydrocarbons to construct various complicated amine frameworks. However, controlling the regioselectivity of these reactions remains a significant challenge. We have developed a method to control arylation reaction sites by modulating the tertiary amine structure in a polar solvent. This approach operates under simple conditions, requiring only a polar solvent to selectively target the methyl group of N-methyl tertiary amines. It facilitates selective arylation across a wide range of trialkylamines substrates, eliminating previous dependencies on restrictive factors such as the use of symmetrical or cyclic trialkylamines, or the need to fine-tune N-alkyl steric hindrance. Notably, a distinct contrast was observed with benzocyclic tertiary amines: the reaction took place at the adjacent methylene group. Nevertheless, this selectivity is reversed upon expansion to an eight-membered ring, wherein the N-methyl group is again favored.
{"title":"Photocatalyzed regioselective arylation of trialkylamines","authors":"Jiamin Wu, Xin Wang, Kuai Wang, Ling-Guo Meng","doi":"10.1039/d5qo01719j","DOIUrl":"https://doi.org/10.1039/d5qo01719j","url":null,"abstract":"Easily available trialkylamines are increasingly utilized as coupling partners with diverse hydrocarbons to construct various complicated amine frameworks. However, controlling the regioselectivity of these reactions remains a significant challenge. We have developed a method to control arylation reaction sites by modulating the tertiary amine structure in a polar solvent. This approach operates under simple conditions, requiring only a polar solvent to selectively target the methyl group of N-methyl tertiary amines. It facilitates selective arylation across a wide range of trialkylamines substrates, eliminating previous dependencies on restrictive factors such as the use of symmetrical or cyclic trialkylamines, or the need to fine-tune N-alkyl steric hindrance. Notably, a distinct contrast was observed with benzocyclic tertiary amines: the reaction took place at the adjacent methylene group. Nevertheless, this selectivity is reversed upon expansion to an eight-membered ring, wherein the N-methyl group is again favored.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"100 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147334523","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The exploration of Z/E stereoisomers represents an interesting and significant endeavor in molecular engineering. We developed three pairs of tetraphenylethylene (TPE) derivatives modified by heteroatom-containing trivalent arylboron and/or tris(2-methylpyridyl)amine (TPA) to explore the differences in the optical properties, morphologies, and sensing applications in the Z and E stereoisomers. They exhibit similar photophysical properties in the solution state, and obvious difference 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-wave fluorescence emission. 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 fluorescent emission of Z-isomer cis-BB should originate from staggerarranged molecular pair, and the green fluorescence of E-isomer trans-BB should originate from the molecular J-type aggregation. In addition, the E isomer trans-BN shows a highly selective and sensitive response to HPO4 2-based on the restriction of intramolecular rotation-induced fluorescence enhancement of TPE and the synergistic coordination effect of triarylboron and metal ion 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 Application","authors":"Han-Jiang Yang, Yatuan Ma, Xinpei Zhong, Xin Yang, You Xu, Xiaoxue Zhang, Zhixin Xiang, Xiujuan Huang, Wenji Wang, Jinyi Wang, Maosen Yuan","doi":"10.1039/d6qo00075d","DOIUrl":"https://doi.org/10.1039/d6qo00075d","url":null,"abstract":"The exploration of Z/E stereoisomers represents an interesting and significant endeavor in molecular engineering. We developed three pairs of tetraphenylethylene (TPE) derivatives modified by heteroatom-containing trivalent arylboron and/or tris(2-methylpyridyl)amine (TPA) to explore the differences in the optical properties, morphologies, and sensing applications in the Z and E stereoisomers. They exhibit similar photophysical properties in the solution state, and obvious difference 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-wave fluorescence emission. 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 fluorescent emission of Z-isomer cis-BB should originate from staggerarranged molecular pair, and the green fluorescence of E-isomer trans-BB should originate from the molecular J-type aggregation. In addition, the E isomer trans-BN shows a highly selective and sensitive response to HPO4 2-based on the restriction of intramolecular rotation-induced fluorescence enhancement of TPE and the synergistic coordination effect of triarylboron and metal ion 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.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147330085","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Oxidation and oxidative reactions are a type of fundamental transformation in organic chemistry, which are indispensable for organic synthesis, especially for the total synthesis of natural products. Although there are many reviews on a specific oxidation reaction or oxidation reagent, a general review on diverse oxidation reactions and oxidation reagents in natural product synthesis has not yet been seen. In this review, we selected some total syntheses published during 2020 to 2025 from selected journals and surveyed the oxidation reactions and oxidative transformations employed thererin to reflect the current status of oxidation reactions. The article is organized by functional groups for oxidation and subcategorized by reagents/methods used in natural product synthesis. Prior to the categorized reactions, we selected ten total syntheses, analysed and commented on all the oxidative transformations involved. The information provided will not only be helpful for the chemists in the field of the total synthesis of natural products and for medicinal chemists to plan their syntheses, but also prompt synthetic organic chemists in general to develop modern oxidation reactions/reagents to suit the increasing needs of sustainable organic synthesis.
{"title":"Oxidation Reactions in the Current Total Synthesis of Natural Products","authors":"Jian-Feng Zheng, Anqi Chen, Yan-Jiao Gao, Pei-Qiang Huang","doi":"10.1039/d6qo00050a","DOIUrl":"https://doi.org/10.1039/d6qo00050a","url":null,"abstract":"Oxidation and oxidative reactions are a type of fundamental transformation in organic chemistry, which are indispensable for organic synthesis, especially for the total synthesis of natural products. Although there are many reviews on a specific oxidation reaction or oxidation reagent, a general review on diverse oxidation reactions and oxidation reagents in natural product synthesis has not yet been seen. In this review, we selected some total syntheses published during 2020 to 2025 from selected journals and surveyed the oxidation reactions and oxidative transformations employed thererin to reflect the current status of oxidation reactions. The article is organized by functional groups for oxidation and subcategorized by reagents/methods used in natural product synthesis. Prior to the categorized reactions, we selected ten total syntheses, analysed and commented on all the oxidative transformations involved. The information provided will not only be helpful for the chemists in the field of the total synthesis of natural products and for medicinal chemists to plan their syntheses, but also prompt synthetic organic chemists in general to develop modern oxidation reactions/reagents to suit the increasing needs of sustainable organic synthesis.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"25 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147319858","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Bicyclo[2.1.1]hexanes (BCHs), 2-oxabicyclo[2.1.1]hexanes (oxaBCHs), and 1- or 2-azabicyclo[2.1.1]hexanes (1- or 2-azaBCHs) are emerging as valuable bioisosteres of meta- and ortho-disubstituted benzenes in drug design. These sp3-rich scaffolds offer conformational rigidity and improved physicochemical properties compared to their flat aromatic counterparts. Historically, a lack of robust synthetic methods for these bicyclic hydrocarbons has limited their widespread application. However, over the past five years, significant advances have been made—primarily through [2π + 2π] cycloadditions of 1,5-dienes and [2π + 2σ] cycloadditions between bicyclo[1.1.0]butanes (BCBs) and π-systems. These approaches have enabled diverse bond disconnections and substitution patterns, allowing for the exploration of a range of exit vectors. This review aims to summarize the methodologies reported between 2020 and early 2025, providing readers with an overview of the synthetic strategies developed and a focus on the exit vectors achieved, ultimately serving as a guide to the currently accessible building blocks.
{"title":"Polysubstituted bicyclo-[2.1.1]-hexanes as benzene isosteres for medicinal chemistry","authors":"Eugenio Roà, Quentin Lefebvre","doi":"10.1039/d5qo01662b","DOIUrl":"https://doi.org/10.1039/d5qo01662b","url":null,"abstract":"Bicyclo[2.1.1]hexanes (BCHs), 2-oxabicyclo[2.1.1]hexanes (oxaBCHs), and 1- or 2-azabicyclo[2.1.1]hexanes (1- or 2-azaBCHs) are emerging as valuable bioisosteres of <em>meta</em>- and <em>ortho</em>-disubstituted benzenes in drug design. These sp<small><sup>3</sup></small>-rich scaffolds offer conformational rigidity and improved physicochemical properties compared to their flat aromatic counterparts. Historically, a lack of robust synthetic methods for these bicyclic hydrocarbons has limited their widespread application. However, over the past five years, significant advances have been made—primarily through [2π + 2π] cycloadditions of 1,5-dienes and [2π + 2σ] cycloadditions between bicyclo[1.1.0]butanes (BCBs) and π-systems. These approaches have enabled diverse bond disconnections and substitution patterns, allowing for the exploration of a range of exit vectors. This review aims to summarize the methodologies reported between 2020 and early 2025, providing readers with an overview of the synthetic strategies developed and a focus on the exit vectors achieved, ultimately serving as a guide to the currently accessible building blocks.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"353 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147319859","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Photochemical and thermal peri-cyclization and cycloreversion reactions of organic polyenes are typically governed by orbital symmetry considerations. Here, we report two aryl-imidazoisoindole derivatives featuring benzene and thiophene rings that undergo reversible photochromic reactions via 10π cyclization and cycloreversion. The synthetic study was fully characterized with NMR, Mass, and X-ray analyses, which are further supported by quantum chemical calculations based on the density functional theory, DFT. Both molecules exhibit a reversible color change under UV and visible light irradiation. Photochemical quantum yields are presented, showing suppression with solvent polarity. The colored ring-closed form displayed a spontaneous fading reaction, whose thermodynamic parameters are well characterized. The thiophene-based substance exhibited a lifetime of 67 hr, which was markedly reduced upon protonation of the imidazole ring. Notably, small amounts of acid markedly enhance the spontaneous fading reaction through a catalytic mechanism. DFT calculations clearly supported the ground-state structures and the major contribution of the neutral mesomeric form in both substances. The reaction pathway and transition state for the thermal reaction are also characterized, which rationally support the major contribution of reversible 10π-photocyclization/cycloreversion reactions.
{"title":"Aryl Imidazoisoindoles for Intrinsic 10π Pericyclic Photochromism with Nonlinear Acid Responsiveness","authors":"Taichi Muto, Chigusa Goto, Shohei Katao, Tsuyoshi Kawai","doi":"10.1039/d6qo00016a","DOIUrl":"https://doi.org/10.1039/d6qo00016a","url":null,"abstract":"Photochemical and thermal peri-cyclization and cycloreversion reactions of organic polyenes are typically governed by orbital symmetry considerations. Here, we report two aryl-imidazoisoindole derivatives featuring benzene and thiophene rings that undergo reversible photochromic reactions via 10π cyclization and cycloreversion. The synthetic study was fully characterized with NMR, Mass, and X-ray analyses, which are further supported by quantum chemical calculations based on the density functional theory, DFT. Both molecules exhibit a reversible color change under UV and visible light irradiation. Photochemical quantum yields are presented, showing suppression with solvent polarity. The colored ring-closed form displayed a spontaneous fading reaction, whose thermodynamic parameters are well characterized. The thiophene-based substance exhibited a lifetime of 67 hr, which was markedly reduced upon protonation of the imidazole ring. Notably, small amounts of acid markedly enhance the spontaneous fading reaction through a catalytic mechanism. DFT calculations clearly supported the ground-state structures and the major contribution of the neutral mesomeric form in both substances. The reaction pathway and transition state for the thermal reaction are also characterized, which rationally support the major contribution of reversible 10π-photocyclization/cycloreversion reactions.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"25 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147319860","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The development of catalyst with a rapid turnover rate under ambient reaction condition is highly desired. Inspired by the biocatalytic systems, the field of charge-driven catalysis provide useful guidelines for designing efficient catalysts. The strategic integration of different non-covalent interactions into the single catalytic system is an interesting phenomenon, that could be engaged effectively for diverse chemical reactions. On this front, here we report charged thioureas with a simple design perspective that offers a significant advantage in terms of catalytic activity by leveraging the unusual combination of σ-hole and H-bond. Incorporation of charge over the thione functionality alters the conformation of H-bonds (E, Z; whereas it mostly exist as Z, Z in thiourea systems), and additionally offers σ-hole interactions for the activation of substrates. The catalyst demonstrated potential activity towards three different classes of organic reactions and resulted good to excellent conversions under room temperature conditions with the advantage of scalability. The charged catalyst exhibited multifold rate acceleration (5 – 40 min) compared to its neutral counterparts (>1 day). Kinetic studies, control experiments, computational analysis and mechanistic investigations supports the remarkable catalytic activity.
{"title":"Interactions beyond H-bond: Unveiling the role of unorthodox non-covalent interactions in charged thiourea and its catalytic efficiency","authors":"Prabhahar Murugan, Parul Rathour, Dipankar Das, Brijesh Patel, Srinu Tothadi, Biswajit Ganguly, Saravanan Subramanian","doi":"10.1039/d5qo01735a","DOIUrl":"https://doi.org/10.1039/d5qo01735a","url":null,"abstract":"The development of catalyst with a rapid turnover rate under ambient reaction condition is highly desired. Inspired by the biocatalytic systems, the field of charge-driven catalysis provide useful guidelines for designing efficient catalysts. The strategic integration of different non-covalent interactions into the single catalytic system is an interesting phenomenon, that could be engaged effectively for diverse chemical reactions. On this front, here we report charged thioureas with a simple design perspective that offers a significant advantage in terms of catalytic activity by leveraging the unusual combination of σ-hole and H-bond. Incorporation of charge over the thione functionality alters the conformation of H-bonds (E, Z; whereas it mostly exist as Z, Z in thiourea systems), and additionally offers σ-hole interactions for the activation of substrates. The catalyst demonstrated potential activity towards three different classes of organic reactions and resulted good to excellent conversions under room temperature conditions with the advantage of scalability. The charged catalyst exhibited multifold rate acceleration (5 – 40 min) compared to its neutral counterparts (>1 day). Kinetic studies, control experiments, computational analysis and mechanistic investigations supports the remarkable catalytic activity.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"70 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147334524","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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":"https://doi.org/10.1039/d5qo01752a","url":null,"abstract":"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<small><sub>2</sub></small> 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.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"98 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147320186","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Shibo Lin, Ya Zou, Yiwen Chu, Junfeng Deng, Lifeng Zhao
Atropisomeric architectures with a chiral axis are prevalent in biologically active molecules and natural products, and they are widely put to use in privileged catalysts and chiral ligands. Axially chiral biaryls and heterobiaryls are a fundamental category of atropisomeric compounds with internal barriers caused by rotational restrictions around carbon-carbon, carbon-nitrogen or nitrogen-nitrogen axes. In this regard, the synthesis of biaryls/hetero-biaryls has witnessed substantial progress, despite the generally complicated traditional synthetic methods. Recent developments in the transition metal-catalyzed substrate activation and subsequent annulation reaction offer a straightforward approach to the preparation of various cyclic (hetero)biaryl atropisomers. In this account, we would like to present recent research advancements in transition metal-catalyzed enantioselective annulation reactions towards (hetero)biaryls featuring atropisomeric optical activity. The focus will be on mechanistic investigations, reaction limitations, and synthetic applications. Additionally, the combination of developing synthetic strategies and representative frameworks is discussed, along with some insights into the developing trend.
{"title":"Enantioselective synthesis of atropisomeric biaryls and heterobiaryls via transition metal-catalyzed cyclization","authors":"Shibo Lin, Ya Zou, Yiwen Chu, Junfeng Deng, Lifeng Zhao","doi":"10.1039/d5qo01492a","DOIUrl":"https://doi.org/10.1039/d5qo01492a","url":null,"abstract":"Atropisomeric architectures with a chiral axis are prevalent in biologically active molecules and natural products, and they are widely put to use in privileged catalysts and chiral ligands. Axially chiral biaryls and heterobiaryls are a fundamental category of atropisomeric compounds with internal barriers caused by rotational restrictions around carbon-carbon, carbon-nitrogen or nitrogen-nitrogen axes. In this regard, the synthesis of biaryls/hetero-biaryls has witnessed substantial progress, despite the generally complicated traditional synthetic methods. Recent developments in the transition metal-catalyzed substrate activation and subsequent annulation reaction offer a straightforward approach to the preparation of various cyclic (hetero)biaryl atropisomers. In this account, we would like to present recent research advancements in transition metal-catalyzed enantioselective annulation reactions towards (hetero)biaryls featuring atropisomeric optical activity. The focus will be on mechanistic investigations, reaction limitations, and synthetic applications. Additionally, the combination of developing synthetic strategies and representative frameworks is discussed, along with some insights into the developing trend.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"38 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147279541","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Boron dipyrromethene (BODIPY) dyes possess excellent photophysical properties and are extensively used in chemical biology and materials science. While peripheral functionalisation of the dipyrromethene core is well established, modification at the boron centre has remained limited. Here, we demonstrate an Au-catalysed modulation of the boron centre, enabling the synthesis of B-spiroBODIPYs with a 1,3-dioxinone moiety on boron. The resulting B-spiroBODIPY exhibits solvent-dependent fluorescence arising from hydrogen-bonding interactions at the carbonyl oxygen on the 1,3-dioxinone moiety, offering a versatile platform for stimulus-responsive fluorescent probes.
{"title":"B-spiroBODIPYs as a fluorophore responsive to hydrogen bond donors","authors":"Aiko Kondo, Hideaki Takano, Hiroshi Shinokubo","doi":"10.1039/d6qo00102e","DOIUrl":"https://doi.org/10.1039/d6qo00102e","url":null,"abstract":"Boron dipyrromethene (BODIPY) dyes possess excellent photophysical properties and are extensively used in chemical biology and materials science. While peripheral functionalisation of the dipyrromethene core is well established, modification at the boron centre has remained limited. Here, we demonstrate an Au-catalysed modulation of the boron centre, enabling the synthesis of B-spiroBODIPYs with a 1,3-dioxinone moiety on boron. The resulting B-spiroBODIPY exhibits solvent-dependent fluorescence arising from hydrogen-bonding interactions at the carbonyl oxygen on the 1,3-dioxinone moiety, offering a versatile platform for stimulus-responsive fluorescent probes.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"37 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147320187","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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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