A 1,3‐iodoesterification of 2‐substituted indoles with trihaloacetic acid, iodination reagent, and hypervalent iodine(III) compound was developed as an acid‐promoted C<sub>sp2</sub>–H/C<sub>sp3</sub>–H dual functionalization reaction to furnish 3‐iodo‐2‐trihaloacetoxymethyl indoles. The one‐pot 1,3‐iodoesterification/hydrolysis of the trihaloester group provided 3‐iodo‐2‐pivaloylmethyl indoles via the rearrangement of the pivaloyl group. The reaction proceeded through a trihaloacetic acid‐assisted electrophilic activation of the iodination reagent after the formation of an indolyl(mesityl)iodonium trihaloacetate.
{"title":"1,3‐Iodoesterification of 2‐Substituted Indoles via Csp2–H/Csp3–H Retained Dual Functionalization Using Hypervalent Iodine(III)","authors":"Hiroko Wasaki, Katsuhiko Moriyama","doi":"10.1002/adsc.202401496","DOIUrl":"https://doi.org/10.1002/adsc.202401496","url":null,"abstract":"A 1,3‐iodoesterification of 2‐substituted indoles with trihaloacetic acid, iodination reagent, and hypervalent iodine(III) compound was developed as an acid‐promoted C<sub>sp2</sub>–H/C<sub>sp3</sub>–H dual functionalization reaction to furnish 3‐iodo‐2‐trihaloacetoxymethyl indoles. The one‐pot 1,3‐iodoesterification/hydrolysis of the trihaloester group provided 3‐iodo‐2‐pivaloylmethyl indoles via the rearrangement of the pivaloyl group. The reaction proceeded through a trihaloacetic acid‐assisted electrophilic activation of the iodination reagent after the formation of an indolyl(mesityl)iodonium trihaloacetate.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"1 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986777","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}
Yu Xing, Xiangheng Li, Zihan Ni, Jiajian Guo, Zijun Zhou, Lei Cui, Chunju Li, Jian Li
A cascade reaction involving 2‐isocyanophenyl propargylic ester and 4‐hydroxy‐2H‐chromen‐2‐one has been documented. This reaction leads to the formation of a highly strained cyclopropen‐imine species, thereby offering an efficient route to synthesize quinoline‐fused polycyclic skeletons.
{"title":"Formal [3+1+1+1] annulation of 2‐isocyanophenyl propargylic esters and 4‐hydroxy‐2H‐chromen‐2‐ones: an access to quinoline‐fused polycyclic skeletons","authors":"Yu Xing, Xiangheng Li, Zihan Ni, Jiajian Guo, Zijun Zhou, Lei Cui, Chunju Li, Jian Li","doi":"10.1002/adsc.202401462","DOIUrl":"https://doi.org/10.1002/adsc.202401462","url":null,"abstract":"A cascade reaction involving 2‐isocyanophenyl propargylic ester and 4‐hydroxy‐2H‐chromen‐2‐one has been documented. This reaction leads to the formation of a highly strained cyclopropen‐imine species, thereby offering an efficient route to synthesize quinoline‐fused polycyclic skeletons.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"29 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986778","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}
Jun Sun, Yu Wei, Wenjian Wang, Wen Lin, Chaodong Wang, Jiadi Zhou, Guan Wang, Jianjun Li
Herein, we disclose a readily available phenothiazine derivative as an oxidizing organic photocatalyst, that serves to induce radical cascade sulfonylation/cyclization reaction of enaminones. A variety of 3-sulfonyl chromones have been obtained with moderate to excellent yields. This catalytic platform proceeds under metal-free conditions with a wide substrate scope and broad functional group compatibility, which unlocks the new reactivity of phenothiazine derivatives and adds significant synthetic values to <i>O</i>-heterocycles.
{"title":"Organic Photoredox Catalytic Sulfonylation of Enaminones to Access 3-Sulfonyl Chromones","authors":"Jun Sun, Yu Wei, Wenjian Wang, Wen Lin, Chaodong Wang, Jiadi Zhou, Guan Wang, Jianjun Li","doi":"10.1002/adsc.202401396","DOIUrl":"https://doi.org/10.1002/adsc.202401396","url":null,"abstract":"Herein, we disclose a readily available phenothiazine derivative as an oxidizing organic photocatalyst, that serves to induce radical cascade sulfonylation/cyclization reaction of enaminones. A variety of 3-sulfonyl chromones have been obtained with moderate to excellent yields. This catalytic platform proceeds under metal-free conditions with a wide substrate scope and broad functional group compatibility, which unlocks the new reactivity of phenothiazine derivatives and adds significant synthetic values to <i>O</i>-heterocycles.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"41 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142988329","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}
Mariur Rodriguez Moreno, Mary L. Setelin, Joshua D. Hansen, James L. Corey, Kirt L. Noble, Lillian R. Stillwell, Emily Angell, Olivia A. Stubbs, Jugal Kumawat, Carlos Santiago Muñoz Gomez, Stacey J. Smith, Daniel H. Ess, David Michaelis
The amination of aryl halides with palladium catalysts (Buchwald‐Hartwig amination) is a widely used transformation in synthetic and drug discovery chemistry. In this report, we demonstrate that a monometallic 2‐phosphinoimidazole Pd catalyst exhibits comparable or enhanced reactivity when compared to all ligands screened for room temperature amination of aryl chlorides with secondary amines. The di‐tert‐butylphosphine derivative showed extremely high reactivity while the di‐isopropyl variant led to almost complete loss of catalytic activity. Computational and experimental mechanistic and kinetic studies indicate that a monometallic Pd structure rather than a bimetallic Pd structure is key to fast catalysis. The di‐tert‐butylphosphine ligand has fast catalysis because it thermodynamically disfavors the formation of a much less active bimetallic Pd complex. A wide substrate scope is demonstrated for the arylation of secondary amines with aryl chlorides using our new catalyst system.
{"title":"Controlling Catalyst Speciation to Achieve Room Temperature Pd‐Catalyzed Aminations with Aryl and Heteroaryl Chlorides","authors":"Mariur Rodriguez Moreno, Mary L. Setelin, Joshua D. Hansen, James L. Corey, Kirt L. Noble, Lillian R. Stillwell, Emily Angell, Olivia A. Stubbs, Jugal Kumawat, Carlos Santiago Muñoz Gomez, Stacey J. Smith, Daniel H. Ess, David Michaelis","doi":"10.1002/adsc.202401337","DOIUrl":"https://doi.org/10.1002/adsc.202401337","url":null,"abstract":"The amination of aryl halides with palladium catalysts (Buchwald‐Hartwig amination) is a widely used transformation in synthetic and drug discovery chemistry. In this report, we demonstrate that a monometallic 2‐phosphinoimidazole Pd catalyst exhibits comparable or enhanced reactivity when compared to all ligands screened for room temperature amination of aryl chlorides with secondary amines. The di‐tert‐butylphosphine derivative showed extremely high reactivity while the di‐isopropyl variant led to almost complete loss of catalytic activity. Computational and experimental mechanistic and kinetic studies indicate that a monometallic Pd structure rather than a bimetallic Pd structure is key to fast catalysis. The di‐tert‐butylphosphine ligand has fast catalysis because it thermodynamically disfavors the formation of a much less active bimetallic Pd complex. A wide substrate scope is demonstrated for the arylation of secondary amines with aryl chlorides using our new catalyst system.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"1 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986776","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, an iron-catalyzed protocol for the aromatization-driven deconstruction and decarboxylation of ketone-derived dihydroquinazolinones in reaction with unsaturated carboxylic acids is reported. A diverse range of fluoroacrylic acids and cinnamic acids reacted effectively with dihydroquinazolinones, yielding essential monofluoroalkenes and alkenes with excellent stereoselectivity. Additionally, spiro-dihydroquinazolinones served as suitable substrates, facilitating the synthesis of valuable quinazolin-4(3H)-ones featuring alkene motifs. This protocol is notable for its operational simplicity and versatility, enabling the chemical diversification of active molecules.
{"title":"Iron-Catalyzed Decarboxylative and Deconstructive Cross-Coupling of Acrylic Acids with Ketone-Derived Dihydroquinazolinones","authors":"Xiao-Yu Lu, Meng-Xue Su, Hua-Yi Huang, Yu-Jun Qian, Hai-Lun Sun, Xiang Li, Xin-Ru Hu, Hao-Yu Dong","doi":"10.1002/adsc.202401503","DOIUrl":"https://doi.org/10.1002/adsc.202401503","url":null,"abstract":"Herein, an iron-catalyzed protocol for the aromatization-driven deconstruction and decarboxylation of ketone-derived dihydroquinazolinones in reaction with unsaturated carboxylic acids is reported. A diverse range of fluoroacrylic acids and cinnamic acids reacted effectively with dihydroquinazolinones, yielding essential monofluoroalkenes and alkenes with excellent stereoselectivity. Additionally, spiro-dihydroquinazolinones served as suitable substrates, facilitating the synthesis of valuable quinazolin-4(3H)-ones featuring alkene motifs. This protocol is notable for its operational simplicity and versatility, enabling the chemical diversification of active molecules.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"9 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981646","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}
Yasuhiro Yamashita, Tomoya Hisada, Yuki Sato, Shu Kobayashi
Mg(SPh)2 has been found to be a highly active catalyst in photocatalytic alkylation reactions of active methylene compounds with nonactivated alkenes. The desired reactions proceeded smoothly to afford the corresponding alkylated products in high yields with low catalyst loadings (0.2-0.3 mol%). This protocol is applicable to a continuous-flow system. Notably, magnesium is an earth-abundant metal, and Mg(SPh)2 exhibits higher catalytic activity than the previously reported LiSPh.
{"title":"Mg(SPh)2 as a Catalyst for Efficient Photocatalytic Alkylation Reactions of Active Methylene Compounds with Nonactivated Alkenes","authors":"Yasuhiro Yamashita, Tomoya Hisada, Yuki Sato, Shu Kobayashi","doi":"10.1002/adsc.202401554","DOIUrl":"https://doi.org/10.1002/adsc.202401554","url":null,"abstract":"Mg(SPh)2 has been found to be a highly active catalyst in photocatalytic alkylation reactions of active methylene compounds with nonactivated alkenes. The desired reactions proceeded smoothly to afford the corresponding alkylated products in high yields with low catalyst loadings (0.2-0.3 mol%). This protocol is applicable to a continuous-flow system. Notably, magnesium is an earth-abundant metal, and Mg(SPh)2 exhibits higher catalytic activity than the previously reported LiSPh.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"24 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981645","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 visible-light-induced intramolecular crossed [2 + 2] cycloaddition reaction of allene-tethered alkylidenecyclopropanes was reported in this paper. The reactions were conducted under mild conditions using Iridium(III) catalyst FirPic as a photosensitizer for energy transfer, affording bridged bicyclic alkenes in moderate to good yields with excellent regioselectivity and stereoselectivity through the regulation of substituents at the olefin’s terminal position. Meanwhile, the computational study explained the special region control assisted by sulfonyl radicals in detail.
{"title":"Intramolecular Crossed [2 + 2] Cycloaddition through Visible-light Triplet Sensitization: Expedient Access to Bridged Bicyclic Alkene","authors":"Min Li, Le-Yi Tao, Xin-Tao Gu, Yin Wei, Min Shi","doi":"10.1002/adsc.202401402","DOIUrl":"https://doi.org/10.1002/adsc.202401402","url":null,"abstract":"A visible-light-induced intramolecular crossed [2 + 2] cycloaddition reaction of allene-tethered alkylidenecyclopropanes was reported in this paper. The reactions were conducted under mild conditions using Iridium(III) catalyst FirPic as a photosensitizer for energy transfer, affording bridged bicyclic alkenes in moderate to good yields with excellent regioselectivity and stereoselectivity through the regulation of substituents at the olefin’s terminal position. Meanwhile, the computational study explained the special region control assisted by sulfonyl radicals in detail.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"84 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981651","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}
Pengyu Zhou, pascal retailleau, Vincent Gandon, Arnaud Voituriez, Xavier Guinchard
Allenes tethered to pyrroles undergo Au(I)-catalyzed hydroarylation leading to tetrahydrodiazepines or tetrahydrodiazonines. The regioselectivity of the reaction is governed by both the substitution pattern of the allene and the nature of the Au(I) ligand. Hence, alkyl-gem-disubstituted allenes preferentially lead to tetrahydrodiazepines via 7-exo- cyclizations, while aryl-substituted allenes preferentially lead to tetrahydrodiazonines via 9-endo cyclization when a phosphite ligand is used. Enantioselective reactions have been developed with the SEGPHOS chiral ligand, leading to chiral heterocycles with high enantioselectivity (up to 96% ee). In addition, DFT calculations have streamlined the regioselectivity (7-exo vs 9-endo) of these gold(I)-catalyzed cyclizations.
连接到吡咯上的烯经过Au(I)催化的氢化芳基化反应生成四氢二氮卓类或四氢二氮卓类化合物。反应的区域选择性由烯的取代模式和Au(I)配体的性质共同决定。因此，当使用亚磷酸盐配体时，烷基基双取代烯优先通过7-外环化生成四氢二氮卓类化合物，而芳基取代烯优先通过9-内环化生成四氢重氮类化合物。与SEGPHOS手性配体发生了对映选择性反应，产生了具有高对映选择性（高达96% ee）的手性杂环。此外，DFT计算简化了这些金(I)催化的环化反应的区域选择性（7-exo vs 9-endo）。
{"title":"Au(I)-Catalyzed Regiodivergent Hydroarylation of Allenes for the Synthesis of Tetrahydrodiazepines or Tetrahydrodiazonines","authors":"Pengyu Zhou, pascal retailleau, Vincent Gandon, Arnaud Voituriez, Xavier Guinchard","doi":"10.1002/adsc.202401541","DOIUrl":"https://doi.org/10.1002/adsc.202401541","url":null,"abstract":"Allenes tethered to pyrroles undergo Au(I)-catalyzed hydroarylation leading to tetrahydrodiazepines or tetrahydrodiazonines. The regioselectivity of the reaction is governed by both the substitution pattern of the allene and the nature of the Au(I) ligand. Hence, alkyl-gem-disubstituted allenes preferentially lead to tetrahydrodiazepines via 7-exo- cyclizations, while aryl-substituted allenes preferentially lead to tetrahydrodiazonines via 9-endo cyclization when a phosphite ligand is used. Enantioselective reactions have been developed with the SEGPHOS chiral ligand, leading to chiral heterocycles with high enantioselectivity (up to 96% ee). In addition, DFT calculations have streamlined the regioselectivity (7-exo vs 9-endo) of these gold(I)-catalyzed cyclizations.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"20 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981648","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}
Yasuhiro Yamashita, Rentaro Enokishima, Yoshihiro Ogasawara, Tomoya Hisada, Shu Kobayashi
Photoinduced catalytic alkylation reactions of active methine compounds with nonactivated alkenes have been developed using an organophotocatalyst, a metal Lewis acid, an arylthiol, and an amine base catalyst system. The alkylation reactions proceeded smoothly under ambient conditions with blue light irradiation, affording the desired products bearing quaternary carbon centers in high yields. Furthermore, enantioselective alkylation with an nonactivated alkene was achieved using a chiral Lewis acid.
{"title":"Photoinduced Catalytic Alkylation of Active Methine Compounds with Nonactivated Alkenes Using Yttrium Triflate as a Lewis Acid Catalyst","authors":"Yasuhiro Yamashita, Rentaro Enokishima, Yoshihiro Ogasawara, Tomoya Hisada, Shu Kobayashi","doi":"10.1002/adsc.202401568","DOIUrl":"https://doi.org/10.1002/adsc.202401568","url":null,"abstract":"Photoinduced catalytic alkylation reactions of active methine compounds with nonactivated alkenes have been developed using an organophotocatalyst, a metal Lewis acid, an arylthiol, and an amine base catalyst system. The alkylation reactions proceeded smoothly under ambient conditions with blue light irradiation, affording the desired products bearing quaternary carbon centers in high yields. Furthermore, enantioselective alkylation with an nonactivated alkene was achieved using a chiral Lewis acid.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"68 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981647","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 present the example of iron-catalyzed reductive amination of nitroarenes under the iron/borane system, providing diverse N-heterocycles in moderate to good yields. This transformation has high efficiency, broad substrate scope, and good functional group compatibility. Preliminary mechanistic studies indicate that hydroxylamines derived from nitrosoarenes may serve as crucial intermediates rather than anilines, and free organic radicals may not participate in the catalytic cycle.
{"title":"Iron-Catalyzed Reductive Deoxygenation of Nitroarenes to Access N-heterocycles","authors":"Zhang Feng, Ziyi Lin, Hong Huang, Ruichen Zhang, Pengjie Xian, Bohao Guo, Chang Qiao","doi":"10.1002/adsc.202401531","DOIUrl":"https://doi.org/10.1002/adsc.202401531","url":null,"abstract":"Herein, we present the example of iron-catalyzed reductive amination of nitroarenes under the iron/borane system, providing diverse N-heterocycles in moderate to good yields. This transformation has high efficiency, broad substrate scope, and good functional group compatibility. Preliminary mechanistic studies indicate that hydroxylamines derived from nitrosoarenes may serve as crucial intermediates rather than anilines, and free organic radicals may not participate in the catalytic cycle.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"29 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142967976","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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