Pub Date : 2024-12-26DOI: 10.1021/acs.orglett.4c04395
Xin Liu, Siyi Chen, Jun Huang, Peiyao Liang, Liejin Zhou, Shoulei Wang
Isothiourea-catalyzed multicomponent cascade reactions are challenging due to the existence of competitive side reactions between multiple reaction partners and intermediates. Herein, we report a practical and efficient protocol for the stereoselective divergent synthesis of pyrazolone-derived β-amino acid esters and β-lactams by isothiourea catalysis. Two distinct reaction pathways are identified, which are controlled by esterification or lactamization of the zwitterionic intermediate. The strategy is attractive because of the convenient one-step procedure, mild conditions, high stereoselectivity, and good functional-group tolerance.
{"title":"Stereoselective Divergent Synthesis of Chiral Pyrazolone Derivatives via Multicomponent Cascade Reactions by Isothiourea Catalysis","authors":"Xin Liu, Siyi Chen, Jun Huang, Peiyao Liang, Liejin Zhou, Shoulei Wang","doi":"10.1021/acs.orglett.4c04395","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04395","url":null,"abstract":"Isothiourea-catalyzed multicomponent cascade reactions are challenging due to the existence of competitive side reactions between multiple reaction partners and intermediates. Herein, we report a practical and efficient protocol for the stereoselective divergent synthesis of pyrazolone-derived β-amino acid esters and β-lactams by isothiourea catalysis. Two distinct reaction pathways are identified, which are controlled by esterification or lactamization of the zwitterionic intermediate. The strategy is attractive because of the convenient one-step procedure, mild conditions, high stereoselectivity, and good functional-group tolerance.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"25 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142888170","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}
Pub Date : 2024-12-25DOI: 10.1021/acs.orglett.4c03917
Komal Goel, Gedu Satyanarayana
This study demonstrates quick access to heteroatom-embodied complex fused polycyclic frameworks through a palladium-catalyzed domino process facilitated by microwave-assisted crossover annulation of o-alkynylarylhalides and dihydrobenzofurans derivatives. The overall success of this process lies in the careful design of dihydrobenzofuran precursors that direct the initial palladium-mediated annulation step to proceed in a highly regioselective manner to furnish a single regioisomeric product. Notably, this one-pot method has witnessed good substrate scope and has furnished products with excellent yields.
{"title":"Microwave-Assisted Palladium-Catalyzed Crossover-Annulation: Access to Fused Polycyclic Benzofuran Scaffolds","authors":"Komal Goel, Gedu Satyanarayana","doi":"10.1021/acs.orglett.4c03917","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c03917","url":null,"abstract":"This study demonstrates quick access to heteroatom-embodied complex fused polycyclic frameworks through a palladium-catalyzed domino process facilitated by microwave-assisted crossover annulation of <i>o</i>-alkynylarylhalides and dihydrobenzofurans derivatives. The overall success of this process lies in the careful design of dihydrobenzofuran precursors that direct the initial palladium-mediated annulation step to proceed in a highly regioselective manner to furnish a single regioisomeric product. Notably, this one-pot method has witnessed good substrate scope and has furnished products with excellent yields.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"123 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142884762","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}
Pub Date : 2024-12-25DOI: 10.1021/acs.orglett.4c04288
Yuliang Wei, Jiaxi Xu
The cascade reaction of 3-diazo-2-sulfonyliminoindolines and N-methoxymethyl-N-[(trimethylsilyl)methyl]benzylamines generates 2-sulfonylimino-1′,3′,4′,6′-tetrahydro-2’H-spiro[indoline-3,5′-pyrimidine] and spiro[indoline-3,3′-pyrrolidine] derivatives simultaneously under the catalysis of TFA and blue light irradiation. Their formation mechanisms were proposed on the basis of isotope-labeled experiments and HRMS analysis of the controlled experiment mixture, showing new reaction pathways. The current reaction provides a new strategy for the synthesis of biologically important spiro[indoline-3,3′-pyrrolidine]-2-one derivatives.
{"title":"Photo-Promoted Construction of 3-Spiro-2-sulfonylimino-indoline Skeletons via Cascade Reaction","authors":"Yuliang Wei, Jiaxi Xu","doi":"10.1021/acs.orglett.4c04288","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04288","url":null,"abstract":"The cascade reaction of 3-diazo-2-sulfonyliminoindolines and <i>N</i>-methoxymethyl-<i>N</i>-[(trimethylsilyl)methyl]benzylamines generates 2-sulfonylimino-1′,3′,4′,6′-tetrahydro-2’<i>H</i>-spiro[indoline-3,5′-pyrimidine] and spiro[indoline-3,3′-pyrrolidine] derivatives simultaneously under the catalysis of TFA and blue light irradiation. Their formation mechanisms were proposed on the basis of isotope-labeled experiments and HRMS analysis of the controlled experiment mixture, showing new reaction pathways. The current reaction provides a new strategy for the synthesis of biologically important spiro[indoline-3,3′-pyrrolidine]-2-one derivatives.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"32 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142888093","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}
Metal-catalytic conversion of polysulfide reagents is a major challenge in organic synthesis due to its challenging activation modes of multiple S–S bonds. The utilization of aryl di- and trithiosulfonates in nickel-catalyzed reductive coupling with aryl halides has been unexplored. Herein, we unprecedentedly describe PPh3 and Zn-collaborative reduction-induced nickel-catalytic selective C–S coupling of aryl di/trithiosulfonates with aryl halides to access sulfides over common disulfides or trisulfides. Diverse mechanistic studies indicate that the key design of such a reaction could be attributed to the employment of PPh3 and MgCl2, which collaborate with Zn for the improved reduction potential that enables selective reductive cleavage of PhSO2(S)naryl (n = 2, 3) to electrophilic sulfur species for reductive sulfuration in a controllable fashion.
{"title":"Collaborative Reduction-Induced Nickel-Catalytic Selective C–S Coupling of Aryl Di/Trithiosulfonates with Aryl Halides","authors":"Lulu Liu, Jiaqi Hou, Yingying Ma, Wen-Hua Xu, Ji-Quan Liu, Dianhu Zhu","doi":"10.1021/acs.orglett.4c04390","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04390","url":null,"abstract":"Metal-catalytic conversion of polysulfide reagents is a major challenge in organic synthesis due to its challenging activation modes of multiple S–S bonds. The utilization of aryl di- and trithiosulfonates in nickel-catalyzed reductive coupling with aryl halides has been unexplored. Herein, we unprecedentedly describe PPh<sub>3</sub> and Zn-collaborative reduction-induced nickel-catalytic selective C–S coupling of aryl di/trithiosulfonates with aryl halides to access sulfides over common disulfides or trisulfides. Diverse mechanistic studies indicate that the key design of such a reaction could be attributed to the employment of PPh<sub>3</sub> and MgCl<sub>2</sub>, which collaborate with Zn for the improved reduction potential that enables selective reductive cleavage of PhSO<sub>2</sub>(S)<sub><i>n</i></sub>aryl (<i>n</i> = 2, 3) to electrophilic sulfur species for reductive sulfuration in a controllable fashion.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"11 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142887220","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}
Pub Date : 2024-12-25DOI: 10.1021/acs.orglett.4c03454
Xiaoying Cao, Xue Tian, Minmin Liu, Shi-Wu Li
Easily obtainable and efficient chiral C2-symmetric bipyridine-N,N′-dioxide ligands with Ni(OTf)2 were developed for application in catalyzing [3 + 2] cycloaddition reactions to synthesize optically active fused pyrazolidines or pyrazoline derivatives featuring three contiguous stereogenic centers by employing azomethine imines and α,β-unsaturated 2-acyl imidazoles, affording the corresponding adducts with the opposite configuration compared to previous synthetic products in 80–98% yields with 28–99% ee and >20:1 dr. In addition, subsequent amplification experiments and derivative transformations of the product further demonstrated the efficient catalytic performance of the catalyst Ni(II)-bipyridine-N,N′-dioxide complexes and the practicality of this synthesis methodology.
{"title":"Asymmetric Synthesis of Optically Active Pyrazolidines or Pyrazoline Derivatives via Ni(II)-Bipyridine-N,N′-dioxide Complexes","authors":"Xiaoying Cao, Xue Tian, Minmin Liu, Shi-Wu Li","doi":"10.1021/acs.orglett.4c03454","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c03454","url":null,"abstract":"Easily obtainable and efficient chiral <i>C</i><sub>2</sub>-symmetric bipyridine-<i>N</i>,<i>N</i>′-dioxide ligands with Ni(OTf)<sub>2</sub> were developed for application in catalyzing [3 + 2] cycloaddition reactions to synthesize optically active fused pyrazolidines or pyrazoline derivatives featuring three contiguous stereogenic centers by employing azomethine imines and α,β-unsaturated 2-acyl imidazoles, affording the corresponding adducts with the opposite configuration compared to previous synthetic products in 80–98% yields with 28–99% ee and >20:1 dr. In addition, subsequent amplification experiments and derivative transformations of the product further demonstrated the efficient catalytic performance of the catalyst Ni(II)-bipyridine-<i>N</i>,<i>N</i>′-dioxide complexes and the practicality of this synthesis methodology.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"25 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142884760","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}
Pub Date : 2024-12-25DOI: 10.1021/acs.orglett.4c04586
Zhaoqiang Chen, Hui Qian
An efficient dehydrative coupling of propargylic alcohols with diarylphosphine oxides to construct tetrasubstituted allenylphosphoryl compounds in the presence of a Pd/Brønsted acid co-catalyst has been developed. As a benefit from the use of a Brønsted acid, this reaction could perform under mild conditions with excellent yields, accommodating a wide range of functional groups. The potential utility of this method has also been demonstrated.
{"title":"Pd/Brønsted Acid Co-catalyzed Dehydrative Coupling of Propargylic Alcohols with Diarylphosphine Oxides","authors":"Zhaoqiang Chen, Hui Qian","doi":"10.1021/acs.orglett.4c04586","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04586","url":null,"abstract":"An efficient dehydrative coupling of propargylic alcohols with diarylphosphine oxides to construct tetrasubstituted allenylphosphoryl compounds in the presence of a Pd/Brønsted acid co-catalyst has been developed. As a benefit from the use of a Brønsted acid, this reaction could perform under mild conditions with excellent yields, accommodating a wide range of functional groups. The potential utility of this method has also been demonstrated.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"14 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142884765","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}
Pub Date : 2024-12-25DOI: 10.1021/acs.orglett.4c04483
Hyesoo Park, Soumyadeep Roy Chowdhury, Hun Young Kim, Kyungsoo Oh
Aerobic nitro-nitrite isomerization of secondary nitroalkanes is postulated to proceed via the intermediacy of the α-nitro alkyl radical, where the corresponding Nef-type products, ketones, and nitrogen monoxide can be obtained as byproducts. To explore the catalytic aerobic carbooximation of alkenes using secondary nitroalkanes, phase-transfer catalysis of KSeCN and TBAI has been developed. The current aerobic carbooximation of alkenes utilizes nitroalkanes as both radical and nitrogen monoxide sources in water without external oxidants and prefunctionalized nitroalkanes.
{"title":"Catalytic Aerobic Carbooximation of Alkenes Using Secondary Nitroalkanes as Both α-Nitro Alkyl Radical and Nitrogen Monoxide Sources","authors":"Hyesoo Park, Soumyadeep Roy Chowdhury, Hun Young Kim, Kyungsoo Oh","doi":"10.1021/acs.orglett.4c04483","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04483","url":null,"abstract":"Aerobic nitro-nitrite isomerization of secondary nitroalkanes is postulated to proceed via the intermediacy of the α-nitro alkyl radical, where the corresponding Nef-type products, ketones, and nitrogen monoxide can be obtained as byproducts. To explore the catalytic aerobic carbooximation of alkenes using secondary nitroalkanes, phase-transfer catalysis of KSeCN and TBAI has been developed. The current aerobic carbooximation of alkenes utilizes nitroalkanes as both radical and nitrogen monoxide sources in water without external oxidants and prefunctionalized nitroalkanes.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"27 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142887221","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}
Pub Date : 2024-12-25DOI: 10.1021/acs.orglett.4c04505
Qigui Nie, Tingting Xu, Xianfu Fang, Yanrong Dan, Gong Zhang, Yangfeng Li, Jianbo Li, Yizhou Li
We here report an efficient DNA-compatible furan–thiol–amine reaction for macrocyclization and late-stage amine transformation. This reaction, conducted under mild conditions, enables the facile cyclization of DNA-conjugated linear peptides into thiopyrrole-grafted macrocycles regardless of ring size or side-chain modification with good to excellent conversion yields. Additionally, this strategy was employed for the late-stage transformation of terminal amines, serving as critical intermediates in the construction of DNA-encoded peptide libraries. Diverse amines were successfully converted into their corresponding thiopyrrole scaffolds, thereby expanding the structural diversity that can be achieved within DNA-encoded libraries.
{"title":"The Furan–Thiol–Amine Reaction Facilitates DNA-Compatible Thiopyrrole-Grafted Macrocyclization and Late-Stage Amine Transformation","authors":"Qigui Nie, Tingting Xu, Xianfu Fang, Yanrong Dan, Gong Zhang, Yangfeng Li, Jianbo Li, Yizhou Li","doi":"10.1021/acs.orglett.4c04505","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04505","url":null,"abstract":"We here report an efficient DNA-compatible furan–thiol–amine reaction for macrocyclization and late-stage amine transformation. This reaction, conducted under mild conditions, enables the facile cyclization of DNA-conjugated linear peptides into thiopyrrole-grafted macrocycles regardless of ring size or side-chain modification with good to excellent conversion yields. Additionally, this strategy was employed for the late-stage transformation of terminal amines, serving as critical intermediates in the construction of DNA-encoded peptide libraries. Diverse amines were successfully converted into their corresponding thiopyrrole scaffolds, thereby expanding the structural diversity that can be achieved within DNA-encoded libraries.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"18 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142887222","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}
Pub Date : 2024-12-25DOI: 10.1021/acs.orglett.4c04209
Vladimir L. Bondarev, Alexey A. Festa, Olga A. Storozhenko, Vladimir A. Kokorekin, Anton P. Novikov, Alexey V. Varlamov, Leonid G. Voskressensky
Electrolysis of o-alkynyl-N-(formyl)anilides and sodium sulfinates on graphite electrodes delivers biologically sound 3-(sulfonyl)quinol-4-ones with moderate to good yields. The reaction is carried out in an undivided cell in the presence of silver(I) oxide with potassium iodide or sodium tetrafluoroborate as the supporting electrolyte. The reaction tolerates variously substituted anilides as well as aryl and alkyl sulfinates. The transformation proceeds as a domino sequence of oxysulfonylation and cyclocondensation steps.
{"title":"Electrochemical Synthesis of 3-(Sulfonyl)quinol-4-ones from o-Alkynyl-N-(formyl)anilides and Sulfinates","authors":"Vladimir L. Bondarev, Alexey A. Festa, Olga A. Storozhenko, Vladimir A. Kokorekin, Anton P. Novikov, Alexey V. Varlamov, Leonid G. Voskressensky","doi":"10.1021/acs.orglett.4c04209","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04209","url":null,"abstract":"Electrolysis of <i>o</i>-alkynyl-<i>N</i>-(formyl)anilides and sodium sulfinates on graphite electrodes delivers biologically sound 3-(sulfonyl)quinol-4-ones with moderate to good yields. The reaction is carried out in an undivided cell in the presence of silver(I) oxide with potassium iodide or sodium tetrafluoroborate as the supporting electrolyte. The reaction tolerates variously substituted anilides as well as aryl and alkyl sulfinates. The transformation proceeds as a domino sequence of oxysulfonylation and cyclocondensation steps.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"70 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142884763","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}
Pub Date : 2024-12-25DOI: 10.1021/acs.orglett.4c03700
Zhi-Yuan Liu, Yan He, Yi-Gang Yang, Ruo-Xing Jin, Shan Zhu, Xi-Sheng Wang
The visible-light-mediated continuous dehydration condensation and oxidative radical dimerization, featuring sulfur hexafluoride (SF6) as both a condensation agent and oxidant, have been developed. This photocatalytic method uses commercially available N-protected amino acids as substrates and enables the formation of azlactone monomers and dimers, facilitating efficient utilization and degradation of greenhouse gas SF6.
{"title":"Visible-Light-Induced Synthesis of Azlactone Monomers and Dimers utilizing SF6 as both Condensation Agent and Oxidant","authors":"Zhi-Yuan Liu, Yan He, Yi-Gang Yang, Ruo-Xing Jin, Shan Zhu, Xi-Sheng Wang","doi":"10.1021/acs.orglett.4c03700","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c03700","url":null,"abstract":"The visible-light-mediated continuous dehydration condensation and oxidative radical dimerization, featuring sulfur hexafluoride (SF<sub>6</sub>) as both a condensation agent and oxidant, have been developed. This photocatalytic method uses commercially available N-protected amino acids as substrates and enables the formation of azlactone monomers and dimers, facilitating efficient utilization and degradation of greenhouse gas SF<sub>6</sub>.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"144 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142887218","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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