Bogdan C. Enache,Anamaria Hanganu,Cristina Tablet,Augustin M. Madalan,Codruta C. Popescu,Mihaela Matache
Photoswitches, molecules that toggle between isomeric forms upon electromagnetic irradiation, have important applications ranging from materials science to pharmacology. Currently, there is a need for photoswitches operated by visible light. We describe the synthesis and characterization of a new class of small-sized, push–pull photoswitches based on aryl azothiadiazole moieties, with excellent visible light switching performance and stable Z isomers. Photoconversion efficiency was found to be concentration-dependent, and we determined an optimal irradiation protocol at λ = 400/550 nm for bidirectional switching. All compounds displayed complex concentration-dependent switching kinetics, which we attribute to solvent interactions or aggregation phenomena in solution. Finally, we used computational chemistry to explain our observations related to absorption and activation barriers for the thermal Z → E back-isomerization. We anticipate that our novel photoswitches will be broadly useful in numerous instances requiring visible light control.
{"title":"Compact and Robust Scaffold for Visible-Light-Actuated Photoswitching","authors":"Bogdan C. Enache,Anamaria Hanganu,Cristina Tablet,Augustin M. Madalan,Codruta C. Popescu,Mihaela Matache","doi":"10.1021/acs.joc.6c01438","DOIUrl":"https://doi.org/10.1021/acs.joc.6c01438","url":null,"abstract":"Photoswitches, molecules that toggle between isomeric forms upon electromagnetic irradiation, have important applications ranging from materials science to pharmacology. Currently, there is a need for photoswitches operated by visible light. We describe the synthesis and characterization of a new class of small-sized, push–pull photoswitches based on aryl azothiadiazole moieties, with excellent visible light switching performance and stable Z isomers. Photoconversion efficiency was found to be concentration-dependent, and we determined an optimal irradiation protocol at λ = 400/550 nm for bidirectional switching. All compounds displayed complex concentration-dependent switching kinetics, which we attribute to solvent interactions or aggregation phenomena in solution. Finally, we used computational chemistry to explain our observations related to absorption and activation barriers for the thermal Z → E back-isomerization. We anticipate that our novel photoswitches will be broadly useful in numerous instances requiring visible light control.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"12 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149275066","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}
Herein, we report a copper-catalyzed, substrate-controlled regiodivergent carboarylation-ring closure of alkynyl benzylphosphonates with diaryliodonium salts. This protocol provides access to a range of 1,2-oxaphosphepine 2-oxides and phosphaisocoumarins in moderate to good yields from the same class of substrates. The electronic nature of the substituent on the alkyne moiety plays a key role in controlling regioselectivity: alkynyl benzylphosphonates bearing electron-donating groups selectively afford 1,2-oxaphosphepine 2-oxides, whereas substrates bearing electron-withdrawing groups furnish the corresponding phosphaisocoumarins.
{"title":"Substrate-Controlled Copper-Catalyzed Regiodivergent Carboarylation-Ring Closure of Alkynyl Benzylphosphonates with Diaryliodonium Salts","authors":"Xingyu Tu,Bo Jiang,Danqing Wu,Xihao Niu,Zihao Jin,Zhiwei Miao","doi":"10.1021/acs.joc.6c01751","DOIUrl":"https://doi.org/10.1021/acs.joc.6c01751","url":null,"abstract":"Herein, we report a copper-catalyzed, substrate-controlled regiodivergent carboarylation-ring closure of alkynyl benzylphosphonates with diaryliodonium salts. This protocol provides access to a range of 1,2-oxaphosphepine 2-oxides and phosphaisocoumarins in moderate to good yields from the same class of substrates. The electronic nature of the substituent on the alkyne moiety plays a key role in controlling regioselectivity: alkynyl benzylphosphonates bearing electron-donating groups selectively afford 1,2-oxaphosphepine 2-oxides, whereas substrates bearing electron-withdrawing groups furnish the corresponding phosphaisocoumarins.","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":"149248753","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}
An efficient and practical protocol has been developed for the synthesis of γ-lactam- and ε-caprolactam-derived thioamides through sulfur-mediated decarboxylative coupling of α,β-unsaturated carboxylic acids with DBN or DBU, accompanied by amidine ring opening. The transformation employs readily available and inexpensive starting materials and proceeds under transition-metal- and external-oxidant-free conditions. Control experiments and mechanistic studies support the involvement of sulfur-derived polysulfide intermediates and subsequent amidine ring opening. The operational simplicity and the use of elemental sulfur make this protocol a useful approach to lactam-derived thioamides.
{"title":"Sulfur-Mediated Decarboxylative Thioamidation of α,β-Unsaturated Carboxylic Acids to Lactam-Derived Thioamides","authors":"Kaushal Kishor,Shiv Chand,Mayank Murthy,Krishna Nand Singh","doi":"10.1021/acs.joc.6c01746","DOIUrl":"https://doi.org/10.1021/acs.joc.6c01746","url":null,"abstract":"An efficient and practical protocol has been developed for the synthesis of γ-lactam- and ε-caprolactam-derived thioamides through sulfur-mediated decarboxylative coupling of α,β-unsaturated carboxylic acids with DBN or DBU, accompanied by amidine ring opening. The transformation employs readily available and inexpensive starting materials and proceeds under transition-metal- and external-oxidant-free conditions. Control experiments and mechanistic studies support the involvement of sulfur-derived polysulfide intermediates and subsequent amidine ring opening. The operational simplicity and the use of elemental sulfur make this protocol a useful approach to lactam-derived thioamides.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"17 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-10-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149241615","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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