Phosgene remains a privileged reagent for carbonylation; however, its extreme toxicity and stringent regulatory controls often restrict its routine and broad application. Herein, we describe a unified CO2-based carbonylation platform for the synthesis of ureas, (thio)carbamates, (thio)carbonates, amides, and formamides under mild, metal-free conditions. The method employs readily available phosphorus(V) activators to generate transient phosphorus-activated carbonyl species that selectively react with amines, alcohols, thiols, hydrides, and organometallic reagents, enabling a one-pot, three-component protocol that telescopes multi-step phosgene-based sequences into a single operation. This approach eliminates the need for phosgene and other preactivated carbonylating reagents. Mechanistic studies are most consistent with the involvement of a transient phosphorus-mediated carbonylating species, conceptually analogous to electrophilic carbonyl transfer in biological systems, although its precise identity remains unresolved. The synthetic utility of the platform is demonstrated by the 25 g synthesis of the anticancer drug sorafenib using POCl3 as the activator. By harnessing CO2 as a C1 synthon, this strategy addresses a long-standing challenge in electrophilic carbonylation and provides an operationally simple and complementary alternative to phosgene-based methods.
{"title":"A Unified Phosgene-Free Carbonylation Using CO2 for the Synthesis of Ureas, Carbamates, Carbonates, Amides, and Formamides","authors":"Lalit Malkania,Arun Kumar,Varun Kumar,Anil Rana,Pankaj Sharma,Nutan Sharma,Nidhi Sharma,Naveen Yadav,Dinesh Mahajan","doi":"10.1021/acs.joc.6c01831","DOIUrl":"https://doi.org/10.1021/acs.joc.6c01831","url":null,"abstract":"Phosgene remains a privileged reagent for carbonylation; however, its extreme toxicity and stringent regulatory controls often restrict its routine and broad application. Herein, we describe a unified CO2-based carbonylation platform for the synthesis of ureas, (thio)carbamates, (thio)carbonates, amides, and formamides under mild, metal-free conditions. The method employs readily available phosphorus(V) activators to generate transient phosphorus-activated carbonyl species that selectively react with amines, alcohols, thiols, hydrides, and organometallic reagents, enabling a one-pot, three-component protocol that telescopes multi-step phosgene-based sequences into a single operation. This approach eliminates the need for phosgene and other preactivated carbonylating reagents. Mechanistic studies are most consistent with the involvement of a transient phosphorus-mediated carbonylating species, conceptually analogous to electrophilic carbonyl transfer in biological systems, although its precise identity remains unresolved. The synthetic utility of the platform is demonstrated by the 25 g synthesis of the anticancer drug sorafenib using POCl3 as the activator. By harnessing CO2 as a C1 synthon, this strategy addresses a long-standing challenge in electrophilic carbonylation and provides an operationally simple and complementary alternative to phosgene-based methods.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"33 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149251014","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}
We have developed a Bi(OTf)3-catalyzed three-component Povarov reaction of aminoquinones, aldehydes, and olefins that provides straightforward, one-step access to highly substituted 1,2,3,4-tetrahydroquinolinequinones in isolated yields of up to 96%, with diastereoselectivities ranging from 1.6:1 to >20:1. Mechanistic studies using E- and Z-alkene probes support a stepwise cationic pathway rather than a concerted cycloaddition, which rationalizes the observed stereochemical outcomes. The synthetic utility is further highlighted by subsequent oxidative dehydrogenation to afford quinolinequinone derivatives, a class of molecules of significant biological relevance.
{"title":"Bi(OTf)3-Catalyzed Diastereoselective Three-Component Povarov Reaction of Aminoquinones toward Tetrahydroquinolinequinones","authors":"Guixuan Zhao,Shaozhong Wang","doi":"10.1021/acs.joc.6c01919","DOIUrl":"https://doi.org/10.1021/acs.joc.6c01919","url":null,"abstract":"We have developed a Bi(OTf)3-catalyzed three-component Povarov reaction of aminoquinones, aldehydes, and olefins that provides straightforward, one-step access to highly substituted 1,2,3,4-tetrahydroquinolinequinones in isolated yields of up to 96%, with diastereoselectivities ranging from 1.6:1 to >20:1. Mechanistic studies using E- and Z-alkene probes support a stepwise cationic pathway rather than a concerted cycloaddition, which rationalizes the observed stereochemical outcomes. The synthetic utility is further highlighted by subsequent oxidative dehydrogenation to afford quinolinequinone derivatives, a class of molecules of significant biological relevance.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"3 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149251001","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}
A facile one-pot electrochemically induced addition–cyclization reaction of isocyanides, amines, and trimethylsilyl azide (TMSN3) has been established for the construction of diversely substituted 5-aminotetrazoles. This protocol enables efficient C–N and N–N bond formation under mild conditions, avoiding transition-metal catalysts and external oxidants. The reaction exhibits a broad substrate scope and good functional group compatibility, while a gram-scale experiment demonstrates the scalability of this electrochemical protocol.
{"title":"Electrochemically Induced Three-Component Synthesis of Substituted 5-Aminotetrazoles from Isocyanides, Amines, and Azides","authors":"Hong-Yu Wu,Bing Li,Lin Zhang,Jun Luo","doi":"10.1021/acs.joc.6c01999","DOIUrl":"https://doi.org/10.1021/acs.joc.6c01999","url":null,"abstract":"A facile one-pot electrochemically induced addition–cyclization reaction of isocyanides, amines, and trimethylsilyl azide (TMSN3) has been established for the construction of diversely substituted 5-aminotetrazoles. This protocol enables efficient C–N and N–N bond formation under mild conditions, avoiding transition-metal catalysts and external oxidants. The reaction exhibits a broad substrate scope and good functional group compatibility, while a gram-scale experiment demonstrates the scalability of this electrochemical protocol.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"79 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149251015","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}
Sanoop P. Chandrasekharan,Usha Yadav,Indrajith K. Biju,Shreeya Srivastava,Kishor Mohanan
The work reported herein details a generalized [3 + 3] annulation approach for the construction of an important class of difluorinated δ-lactam motifs using α-fluoroacetamides and 2-CF3-1,3-enynes. The key to this advancement lies in the strategic use of α-fluoro-β-ketoamide as a 1,3-binucleophilic synthon and 2-CF3-1,3-enyne as a 1,3-dielectrophilic species. Mechanistically, the reaction proceeds through a sequential nucleophilic substitution of an allylic fluorine atom (SN2′) followed by a ring-closing nucleophilic vinylic fluorine atom substitution (SNV) cascade, involving α-fluoroacetamides and CF3-enynes. Moreover, we successfully leveraged α-fluoromalonamates as a useful 1,3-binucleophilic synthon in place of α-fluoroacetamides.
{"title":"Defluorinative [3 + 3] Annulation Reaction of α-Fluoroacetamides with 2-Trifluoromethylalkenes for the Formation of Densely Functionalized Difluorinated δ-Lactams","authors":"Sanoop P. Chandrasekharan,Usha Yadav,Indrajith K. Biju,Shreeya Srivastava,Kishor Mohanan","doi":"10.1021/acs.joc.6c01845","DOIUrl":"https://doi.org/10.1021/acs.joc.6c01845","url":null,"abstract":"The work reported herein details a generalized [3 + 3] annulation approach for the construction of an important class of difluorinated δ-lactam motifs using α-fluoroacetamides and 2-CF3-1,3-enynes. The key to this advancement lies in the strategic use of α-fluoro-β-ketoamide as a 1,3-binucleophilic synthon and 2-CF3-1,3-enyne as a 1,3-dielectrophilic species. Mechanistically, the reaction proceeds through a sequential nucleophilic substitution of an allylic fluorine atom (SN2′) followed by a ring-closing nucleophilic vinylic fluorine atom substitution (SNV) cascade, involving α-fluoroacetamides and CF3-enynes. Moreover, we successfully leveraged α-fluoromalonamates as a useful 1,3-binucleophilic synthon in place of α-fluoroacetamides.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"2 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149251013","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}
We have developed a selective dehalogenative amination of 4-bromo-1,1,2-trifluoro-1-butene with nitrogen-containing heteroarenes, furnishing a series of N-difluorovinyl heteroarenes with excellent regioselectivity and stereoselectivity. This methodology is free of high-pressure acetylene or transition-metal catalysis, and delivers high yields. It displays good substrate compatibility with a variety of nitrogen heterocycles, including indole, benzimidazole, benzotriazole, and carbazole.
{"title":"Dehalogenative Regiospecific Amination of 4-Bromo-1,1,2-trifluoro-1-butene with N-Heterocycles: Synthesis of 1,2-Difluorobuta-1,3-dien-1-yl Azaarenes","authors":"Huiting Zhou,Caihong Ning,Guangkai Yao,Chen Zhao,Hanhong Xu,Chuanle Zhu","doi":"10.1021/acs.joc.6c01444","DOIUrl":"https://doi.org/10.1021/acs.joc.6c01444","url":null,"abstract":"We have developed a selective dehalogenative amination of 4-bromo-1,1,2-trifluoro-1-butene with nitrogen-containing heteroarenes, furnishing a series of N-difluorovinyl heteroarenes with excellent regioselectivity and stereoselectivity. This methodology is free of high-pressure acetylene or transition-metal catalysis, and delivers high yields. It displays good substrate compatibility with a variety of nitrogen heterocycles, including indole, benzimidazole, benzotriazole, and carbazole.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"10 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149251012","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}
Ayana Sakura,Yumiko Koseki,Daiki Noguchi,Kazuhiro Yoshida
A new set of reaction conditions for the rhodium-catalyzed enantioselective C–H bond amination of 1,3-disubstituted adamantanes has been developed. An amino acid derivative bearing a bromide substituent was obtained in up to 90% ee through enantioselective desymmetrization. The protocol was also applicable to substrates bearing chloride, methyl, and butyl substituents, affording the corresponding amino acid derivatives in >80% ee. The bromide-containing product was further converted into chloride and azide derivatives, demonstrating its utility as a chiral building block.
{"title":"Enantioselective Synthesis of Halogenated Adamantane-Based Amino Acid Derivatives via Rhodium-Catalyzed C–H Bond Amination","authors":"Ayana Sakura,Yumiko Koseki,Daiki Noguchi,Kazuhiro Yoshida","doi":"10.1021/acs.joc.6c01914","DOIUrl":"https://doi.org/10.1021/acs.joc.6c01914","url":null,"abstract":"A new set of reaction conditions for the rhodium-catalyzed enantioselective C–H bond amination of 1,3-disubstituted adamantanes has been developed. An amino acid derivative bearing a bromide substituent was obtained in up to 90% ee through enantioselective desymmetrization. The protocol was also applicable to substrates bearing chloride, methyl, and butyl substituents, affording the corresponding amino acid derivatives in >80% ee. The bromide-containing product was further converted into chloride and azide derivatives, demonstrating its utility as a chiral building block.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"2 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149251009","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}
Josie Ascione,Gordon Farley,Rodrigo De Leon,Sheila Namirembe,Brian Carvalho,Michael Chaoui,Henry Noe,Michael Beauchamp,André K. Isaacs
A general approach to the synthesis of 7-azabicyclo[4.2.0]octadienes was achieved via the Cu-catalyzed azide-alkyne cycloaddition (CuAAC) of readily accessible carbon- and oxygen-based 1,6-diynes synthesized in two steps starting from aldehydes/ketones or alkylidene malonates. The reaction proceeds through a probable [2 + 2] cycloaddition reaction of an activated alkyne with the C═N bond of a CuAAC-generated ketenimine intermediate. This underexplored mode of ketenimine reactivity provides rapid access to fused 2-azetines and expands the scope of carbon-based π-nucleophiles capable of intercepting CuAAC-generated ketenimines.
{"title":"Intramolecular [2 + 2] Cycloaddition of Cu-Catalyzed Azide–Alkyne Cycloaddition Generated Ketenimines and Alkoxyalkynes for the Synthesis of 7-Azabicyclo[4.2.0]octa-1(8),5-dienes","authors":"Josie Ascione,Gordon Farley,Rodrigo De Leon,Sheila Namirembe,Brian Carvalho,Michael Chaoui,Henry Noe,Michael Beauchamp,André K. Isaacs","doi":"10.1021/acs.joc.6c01771","DOIUrl":"https://doi.org/10.1021/acs.joc.6c01771","url":null,"abstract":"A general approach to the synthesis of 7-azabicyclo[4.2.0]octadienes was achieved via the Cu-catalyzed azide-alkyne cycloaddition (CuAAC) of readily accessible carbon- and oxygen-based 1,6-diynes synthesized in two steps starting from aldehydes/ketones or alkylidene malonates. The reaction proceeds through a probable [2 + 2] cycloaddition reaction of an activated alkyne with the C═N bond of a CuAAC-generated ketenimine intermediate. This underexplored mode of ketenimine reactivity provides rapid access to fused 2-azetines and expands the scope of carbon-based π-nucleophiles capable of intercepting CuAAC-generated ketenimines.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"79 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149248755","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}
A series of 2H-chromene indole derivatives containing 4-position substituted C–N axially chiral indole and 2-position central chiral trifluoromethyl were synthesized through a Pd-catalyzed asymmetric condensation reaction combined with the strategy of converting central chirality to axial chirality via double-bond isomerization. This method is simple to operate, with a yield of up to 89% and an enantioselectivity of up to 97% enantiomeric excess (ee).
{"title":"Synthesis of 4-Substituted C–N Axially Chiral 2-(Trifluoromethyl)-2H-chromene Indole Derivatives via Central-to-Axial Chirality Conversion","authors":"Pengyue Zhang,Bangzhong Wang,Jianzhang Cheng,Quanyi Liu,Jinfeng Zhao,Jingping Qu,Nan Cai,Yuhan Zhou","doi":"10.1021/acs.joc.6c01902","DOIUrl":"https://doi.org/10.1021/acs.joc.6c01902","url":null,"abstract":"A series of 2H-chromene indole derivatives containing 4-position substituted C–N axially chiral indole and 2-position central chiral trifluoromethyl were synthesized through a Pd-catalyzed asymmetric condensation reaction combined with the strategy of converting central chirality to axial chirality via double-bond isomerization. This method is simple to operate, with a yield of up to 89% and an enantioselectivity of up to 97% enantiomeric excess (ee).","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"21 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-10-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149241612","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}
The development of novel catalytic transformations that repurpose classical reagents to directly access structurally diverse products from the same starting materials has garnered significant interest. By eliminating the need to separately synthesize and purify new reagents, the chemical space reachable from existing functionalized intermediates can be increased multifold. Nitrogen insertion strategies can convert the C–C bond formed in traditional Suzuki–Miyaura coupling into a C–N–C bond, substantially expanding the explorable chemical space. Herein, building upon the arylthianthrenium salt strategy, we have developed a room-temperature palladium-catalyzed nitrogen-atom insertion coupling reaction, providing a new retrosynthetic disconnection strategy that can be directly applied to the late-stage functionalization (LSF) of complex drug molecules. Notably, this intermolecular three-component aminative coupling proceeds smoothly at room temperature, which not only aligns with the principles of green chemistry by obviating the need for heating apparatus and light-irradiation equipment, but also reduces energy consumption while enhancing reaction safety. To probe the mechanism, control experiments were conducted, and the catalytic reaction was monitored by NMR spectroscopy. Based on these results and density functional theory (DFT) calculations, the barrier for the overall rate-determining step is only 16.5 kcal/mol, explaining the room-temperature reactivity.
{"title":"Room-Temperature Palladium-Catalyzed Aminative Suzuki–Miyaura Coupling of Arylthianthrenium Salts and Mechanistic Studies","authors":"Bo-Sheng Zhang,Xin-Yue Fu,Feng Zhang,Long-Sheng Wang,Ke-Hu Wang,Xi-Cun Wang,Xue-Ya Gou,Yulai Hu,Yong-Min Liang","doi":"10.1021/acs.joc.6c02280","DOIUrl":"https://doi.org/10.1021/acs.joc.6c02280","url":null,"abstract":"The development of novel catalytic transformations that repurpose classical reagents to directly access structurally diverse products from the same starting materials has garnered significant interest. By eliminating the need to separately synthesize and purify new reagents, the chemical space reachable from existing functionalized intermediates can be increased multifold. Nitrogen insertion strategies can convert the C–C bond formed in traditional Suzuki–Miyaura coupling into a C–N–C bond, substantially expanding the explorable chemical space. Herein, building upon the arylthianthrenium salt strategy, we have developed a room-temperature palladium-catalyzed nitrogen-atom insertion coupling reaction, providing a new retrosynthetic disconnection strategy that can be directly applied to the late-stage functionalization (LSF) of complex drug molecules. Notably, this intermolecular three-component aminative coupling proceeds smoothly at room temperature, which not only aligns with the principles of green chemistry by obviating the need for heating apparatus and light-irradiation equipment, but also reduces energy consumption while enhancing reaction safety. To probe the mechanism, control experiments were conducted, and the catalytic reaction was monitored by NMR spectroscopy. Based on these results and density functional theory (DFT) calculations, the barrier for the overall rate-determining step is only 16.5 kcal/mol, explaining the room-temperature reactivity.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"5 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-10-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149241895","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}
A one-pot annulative Suzuki–Miyaura strategy was developed for the synthesis of highly fluorescent, near-infrared (NIR)-emissive polycyclic aromatic hydrocarbon (PAH)-fused BODIPYs. Tetrahalogenated BODIPYs reacted with 1,2-bis(pinacolato)boryl arene or alkene via a fourfold cross-coupling/annulation cascade under Pd(PPh3)4 catalysis, furnishing phenanthro[b]- or naphtho[b]-fused products in 32–70% yields without isolation of intermediates. Single-crystal X-ray diffraction revealed slightly twisted frameworks (dihedral angles: 3.17–10.01°), and NICS(0) calculations confirmed strong local aromaticity. Photophysical studies displayed intense absorption at 658–675 nm and narrow NIR emission at 670–690 nm, together with small Stokes shifts (≤322 cm–1) and high fluorescence quantum yields (ΦF = 0.46–0.68). Their weak solvatochromism and substantial HOMO–LUMO overlap indicate that the emissive excited states are predominantly locally excited (LE) in character. Cyclic voltammetry demonstrated narrow electrochemical band gaps (1.51–1.70 eV) and low LUMO energy levels (–3.82 to –3.88 eV for 3a–c and 4e), while DFT and TD-DFT calculations showed that the lowest-energy excitation is dominated by a HOMO → LUMO π → π* transition. This modular annulation strategy provides concise access to rigid PAH-fused BODIPYs that combine efficient NIR emission with high fluorescence efficiency, offering a versatile platform for the development of advanced NIR fluorophores.
{"title":"Annulative Suzuki–Miyaura Coupling for the Synthesis of Highly Fluorescent Near-Infrared PAH[b]-Fused BODIPYs","authors":"Xiaowei Zhang,Yongli Zhang,Peixin Li,Ruihan Yang,Yanni Li,Yunfei Zhi,Tianding Hu,Shaoyun Shan,Yanhua Yang,Xiangguang Li","doi":"10.1021/acs.joc.6c01809","DOIUrl":"https://doi.org/10.1021/acs.joc.6c01809","url":null,"abstract":"A one-pot annulative Suzuki–Miyaura strategy was developed for the synthesis of highly fluorescent, near-infrared (NIR)-emissive polycyclic aromatic hydrocarbon (PAH)-fused BODIPYs. Tetrahalogenated BODIPYs reacted with 1,2-bis(pinacolato)boryl arene or alkene via a fourfold cross-coupling/annulation cascade under Pd(PPh3)4 catalysis, furnishing phenanthro[b]- or naphtho[b]-fused products in 32–70% yields without isolation of intermediates. Single-crystal X-ray diffraction revealed slightly twisted frameworks (dihedral angles: 3.17–10.01°), and NICS(0) calculations confirmed strong local aromaticity. Photophysical studies displayed intense absorption at 658–675 nm and narrow NIR emission at 670–690 nm, together with small Stokes shifts (≤322 cm–1) and high fluorescence quantum yields (ΦF = 0.46–0.68). Their weak solvatochromism and substantial HOMO–LUMO overlap indicate that the emissive excited states are predominantly locally excited (LE) in character. Cyclic voltammetry demonstrated narrow electrochemical band gaps (1.51–1.70 eV) and low LUMO energy levels (–3.82 to –3.88 eV for 3a–c and 4e), while DFT and TD-DFT calculations showed that the lowest-energy excitation is dominated by a HOMO → LUMO π → π* transition. This modular annulation strategy provides concise access to rigid PAH-fused BODIPYs that combine efficient NIR emission with high fluorescence efficiency, offering a versatile platform for the development of advanced NIR fluorophores.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"25 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-10-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149241899","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}
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