To provide fluorinated allylamines, a visible-light photocatalytic C–F/C–H coupling of easily accessible gem-difluoroalkenes and secondary N-alkylanilines was described. The protocol proceeded under mild conditions, with excellent functional group compatibility and a broad scope including complex natural product derivatives, thus providing a green method for the preparation of high-value functionalized monofluoroalkenes. Mechanistic studies elucidated a photoredox catalyzed radical–radical coupling pathway.
{"title":"Photoredox Catalytic Defluoroalkylation of gem-Difluoroalkenes with Secondary N-Alkylanilines via C–F/C–H Coupling","authors":"Haiyang Hu, Baokai Yang, Yongcan Liu, Wengang Xu, Congjian Xia, Guoqiang Xu, Mingbo Wu","doi":"10.1021/acs.orglett.4c04432","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04432","url":null,"abstract":"To provide fluorinated allylamines, a visible-light photocatalytic C–F/C–H coupling of easily accessible <i>gem</i>-difluoroalkenes and secondary <i>N</i>-alkylanilines was described. The protocol proceeded under mild conditions, with excellent functional group compatibility and a broad scope including complex natural product derivatives, thus providing a green method for the preparation of high-value functionalized monofluoroalkenes. Mechanistic studies elucidated a photoredox catalyzed radical–radical coupling pathway.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"48 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874606","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}
An organophotocatalyzed approach for the chemoselective dealkylation of phenols is developed. This method demonstrates exceptional selectivity toward the cleavage of phenolic ethers over equivalent aliphatic ethers and alkyl benzoates, presenting a broad range of functional group sustainability. This strategy also enables selective debenzylation of phenols in the presence of reduction-sensitive functional groups. Mechanistic studies and photophysical experiments provide evidence for the selective disintegration of C–O bonds through photo-oxidation, facilitated by the oxophilicity of silicon.
{"title":"Organophotoredox-Catalyzed Chemoselective Deprotection for Phenolic Ethers Driven by the Oxophilicity of Silicon","authors":"Tanumoy Mandal, Malekul Islam, Sanju Das, Aznur Azim, Suman De Sarkar","doi":"10.1021/acs.orglett.4c04357","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04357","url":null,"abstract":"An organophotocatalyzed approach for the chemoselective dealkylation of phenols is developed. This method demonstrates exceptional selectivity toward the cleavage of phenolic ethers over equivalent aliphatic ethers and alkyl benzoates, presenting a broad range of functional group sustainability. This strategy also enables selective debenzylation of phenols in the presence of reduction-sensitive functional groups. Mechanistic studies and photophysical experiments provide evidence for the selective disintegration of C–O bonds through photo-oxidation, facilitated by the oxophilicity of silicon.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"53 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874605","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 : 2024-12-21DOI: 10.1021/acs.orglett.4c03902
Aurelia Pastor, Carmen Lopez-Leonardo, Guillermo Cutillas-Font, Alberto Martinez-Cuezva, Marta Marin-Luna, Jose-Antonio Garcia-Lopez, Isabel Saura-Llamas, Mateo Alajarin
Intramolecular reactions between isocyano and iminophosphorane functions yield species containing an embedded 1,3,2-diazaphosphetidine ring, as result of the [2 + 2] cycloaddition of the primary reactive product, the cyclic carbodiimide, with a second unit of reactant. DFT studies reveal a first rate-determining step entailing a [2 + 1] cycloaddition involving the isocyanide carbon atom and the P═N double bond, with the further intervention of a dipolar precursor of the intermediate carbodiimide. The 1,3,2-diazaphosphetidine ring of the final products is shown to be hydrolytically and thermally labile.
{"title":"Unveiling the Phosphine-Mediated N-Transfer from Azide to Isocyanide en Route to Carbodiimides and 4-Imino-1,3,2-diazaphosphetidines","authors":"Aurelia Pastor, Carmen Lopez-Leonardo, Guillermo Cutillas-Font, Alberto Martinez-Cuezva, Marta Marin-Luna, Jose-Antonio Garcia-Lopez, Isabel Saura-Llamas, Mateo Alajarin","doi":"10.1021/acs.orglett.4c03902","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c03902","url":null,"abstract":"Intramolecular reactions between isocyano and iminophosphorane functions yield species containing an embedded 1,3,2-diazaphosphetidine ring, as result of the [2 + 2] cycloaddition of the primary reactive product, the cyclic carbodiimide, with a second unit of reactant. DFT studies reveal a first rate-determining step entailing a [2 + 1] cycloaddition involving the isocyanide carbon atom and the P═N double bond, with the further intervention of a dipolar precursor of the intermediate carbodiimide. The 1,3,2-diazaphosphetidine ring of the final products is shown to be hydrolytically and thermally labile.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"55 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142867614","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}
Herein, we report a DMAP-catalyzed [4 + 2] annulation reaction of hex-5-en-2-ynoates 1 with electron-poor alkenes 2, which affords exocyclic olefinic cyclohexenes 3 in good yields and excellent regio-, diastereo-, and E/Z selectivities. Distinguished from previous allenoate- or alkynoate-based substrates, hex-5-en-2-ynoates 1 use the β- and ε-carbons for the bond formation, presenting new and regiodivergent C4 synthons for Lewis base-catalyzed annulations.
{"title":"DMAP-Catalyzed [4 + 2] Annulation of Hex-5-en-2-ynoates with Electron-Poor Alkenes","authors":"Dongqiu Li, Jiale Wu, LuLu Yang, Shuangshuang Cai, Yuhai Tang, Yang Li, Silong Xu","doi":"10.1021/acs.orglett.4c03842","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c03842","url":null,"abstract":"Herein, we report a DMAP-catalyzed [4 + 2] annulation reaction of hex-5-en-2-ynoates <b>1</b> with electron-poor alkenes <b>2</b>, which affords exocyclic olefinic cyclohexenes <b>3</b> in good yields and excellent regio-, diastereo-, and <i>E</i>/<i>Z</i> selectivities. Distinguished from previous allenoate- or alkynoate-based substrates, hex-5-en-2-ynoates <b>1</b> use the β- and ε-carbons for the bond formation, presenting new and regiodivergent C<sub>4</sub> synthons for Lewis base-catalyzed annulations.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"112 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142867615","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 : 2024-12-20DOI: 10.1021/acs.orglett.4c03808
Shao-Jie Cheng, Xin-Li Zhang, Zhen-Xu Yang, Ai-Hua Wang, Zhi-Shi Ye
An efficient palladium-catalyzed N-allylic alkylation of pyrazoles and unactivated vinylcyclopropanes is demonstrated, affording various N-alkyl pyrazoles in ≤99% yield. This protocol displays high atom economy, a broad range of substrates, and excellent regioselectivity and stereoselectivity. Late-stage modification of bioactive molecules, scaled-up reaction, and divergent derivatization documented the practicability of this methodology. The preliminary mechanistic investigation hinted that the Pd–H species promotes the ring opening of cyclopropanes.
{"title":"Palladium-Catalyzed N-Allylic Alkylation of Pyrazoles and Unactivated Vinylcyclopropanes","authors":"Shao-Jie Cheng, Xin-Li Zhang, Zhen-Xu Yang, Ai-Hua Wang, Zhi-Shi Ye","doi":"10.1021/acs.orglett.4c03808","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c03808","url":null,"abstract":"An efficient palladium-catalyzed <i>N</i>-allylic alkylation of pyrazoles and unactivated vinylcyclopropanes is demonstrated, affording various <i>N</i>-alkyl pyrazoles in ≤99% yield. This protocol displays high atom economy, a broad range of substrates, and excellent regioselectivity and stereoselectivity. Late-stage modification of bioactive molecules, scaled-up reaction, and divergent derivatization documented the practicability of this methodology. The preliminary mechanistic investigation hinted that the Pd–H species promotes the ring opening of cyclopropanes.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"44 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142857761","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 : 2024-12-20DOI: 10.1021/acs.orglett.4c04385
Nerea Álvarez-Llorente, Anton J. Stasyuk, Alberto Diez-Varga, Sergio Ferrero, Miquel Solà, Héctor Barbero, Celedonio M. Álvarez
A method to synthesize cofacial dimeric porphyrins bearing eight corannulene units has been developed. It relies on the stability of octahedral CO-capped Ru(II) complexes linked by N-donor ligands. This specific arrangement provides an optimal scaffold to accommodate fullerenes by imposing corannulene groups at a precise distance and relative orientation. Their capabilities for C60 recognition have been thoroughly assessed, revealing that each system can encapsulate up to four guests, giving rise to a compact supramolecular van der Waals complex echoing a discrete donor–acceptor–donor trilayer offering significant potential properties for further exploitation.
{"title":"Multitopic Corannulene–Porphyrin Hosts for Fullerenes: A Three-Layer Scaffold for Precisely Designed Supramolecular Ensembles","authors":"Nerea Álvarez-Llorente, Anton J. Stasyuk, Alberto Diez-Varga, Sergio Ferrero, Miquel Solà, Héctor Barbero, Celedonio M. Álvarez","doi":"10.1021/acs.orglett.4c04385","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04385","url":null,"abstract":"A method to synthesize cofacial dimeric porphyrins bearing eight corannulene units has been developed. It relies on the stability of octahedral CO-capped Ru(II) complexes linked by N-donor ligands. This specific arrangement provides an optimal scaffold to accommodate fullerenes by imposing corannulene groups at a precise distance and relative orientation. Their capabilities for C<sub>60</sub> recognition have been thoroughly assessed, revealing that each system can encapsulate up to four guests, giving rise to a compact supramolecular van der Waals complex echoing a discrete donor–acceptor–donor trilayer offering significant potential properties for further exploitation.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"1 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142857832","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}
We report an unconventional I2-catalyzed cascade reaction for the synthesis of angular triquinane derivatives with a fused heterocycle skeleton, leveraging enaminones and anilines as simple acyclic precursors. The key to success lies in I2 functioning as a polar-reversal catalyst, which alters the reactivity at the α-position of the enaminone and facilitates the first hexa-functionalization of an enaminone along with the formation of highly congested continuous stereocenters.
{"title":"Iodine as Polarity-Reversal Catalyst: Synthesis of a Fused Heterocycle with Contiguous Stereocenters","authors":"Li-Sheng Wang, Yu-Man Song, You Zhou, Yong-Xing Tang, Chun-Yan Wu, Zhi-Cheng Yu, Hui Zhou, Kai-Lu Zheng, An-Xin Wu","doi":"10.1021/acs.orglett.4c03936","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c03936","url":null,"abstract":"We report an unconventional I<sub>2</sub>-catalyzed cascade reaction for the synthesis of angular triquinane derivatives with a fused heterocycle skeleton, leveraging enaminones and anilines as simple acyclic precursors. The key to success lies in I<sub>2</sub> functioning as a polar-reversal catalyst, which alters the reactivity at the α-position of the enaminone and facilitates the first hexa-functionalization of an enaminone along with the formation of highly congested continuous stereocenters.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"75 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142858140","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}
Page 7820. The Strategic Leading Science and Technology Project of Chinese Academy of Sciences grant was incorrectly referenced as E4JD250301; the correct number is XDC0120102. The full correct Acknowledgment is in this Correction. This study was supported by the Strategic Leading Science and Technology Project of Chinese Academy of Sciences (grant no. XDC0120102), National Key Research and Development Program of China (grant no. 2019YFA0905100 to S.G.), and the Tianjin Synthetic Biotechnology Innovation Capacity Improvement Project (TSBICIP-CXRC-062 to S.G. and TSBICIP-CXRC-069 to C.C.). This article has not yet been cited by other publications.
{"title":"Correction to “Synthetic Nicotinamide Cofactors as Alternatives to NADPH in Imine Reductase-Catalyzed Reactions”","authors":"Wei Kang, Shushan Gao, Jinping Bao, Lujia Yang, Yaqing Ma, Pingyuan Wang, Chang-Yun Wang, Chengsen Cui","doi":"10.1021/acs.orglett.4c04624","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04624","url":null,"abstract":"Page 7820. The Strategic Leading Science and Technology Project of Chinese Academy of Sciences grant was incorrectly referenced as E4JD250301; the correct number is XDC0120102. The full correct Acknowledgment is in this Correction. This study was supported by the Strategic Leading Science and Technology Project of Chinese Academy of Sciences (grant no. XDC0120102), National Key Research and Development Program of China (grant no. 2019YFA0905100 to S.G.), and the Tianjin Synthetic Biotechnology Innovation Capacity Improvement Project (TSBICIP-CXRC-062 to S.G. and TSBICIP-CXRC-069 to C.C.). This article has not yet been cited by other publications.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"18 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142858053","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 : 2024-12-20DOI: 10.1021/acs.orglett.4c04127
Anamika Dhami, Sanoop P. Chandrasekharan, Kishor Mohanan
A Lewis acid-mediated C2-N-trifluoroethylamidation of quinolines, employing quinoline N-oxides, trifluorodiazoethane, and acetonitrile to forge a new class of N-(quinolin-2-yl)-N-(trifluoroethyl)acetamide is presented in this Letter. The reaction proceeds through a carbene generation/nitrile ylide formation/(3 + 2) cycloaddition/rearrangement cascade to furnish quinoline-2-N-(trifluoroethyl)acetamide derivatives in high yields.
{"title":"BF3-Mediated C2-Amidation of Quinoline N-Oxides Employing Trifluorodiazoethane and Acetonitrile: Access to 2-N-(Trifluoroethyl)amidoquinolines","authors":"Anamika Dhami, Sanoop P. Chandrasekharan, Kishor Mohanan","doi":"10.1021/acs.orglett.4c04127","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04127","url":null,"abstract":"A Lewis acid-mediated C2-<i>N-</i>trifluoroethylamidation of quinolines, employing quinoline <i>N-</i>oxides, trifluorodiazoethane, and acetonitrile to forge a new class of <i>N-</i>(quinolin<i>-</i>2-yl)-<i>N-</i>(trifluoroethyl)acetamide is presented in this Letter. The reaction proceeds through a carbene generation/nitrile ylide formation/(3 + 2) cycloaddition/rearrangement cascade to furnish quinoline-2-<i>N-</i>(trifluoroethyl)acetamide derivatives in high yields.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"31 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142867616","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 : 2024-12-20DOI: 10.1021/acs.orglett.4c04388
Kanta Shimotai, Ozora Sasamoto, Masanori Shigeno
In this paper, we report that the use of an alkyl silyl carbonate reagent combined with CsF and 18-crown-6 facilitates efficient direct carboxylations of (hetero)aromatic C–H bonds. This system also enables benzylic carboxylation of a toluene derivative and double carboxylation of methyl heteroarene. The carbonate reagent is characterized by its ease of handling and storage. Moreover, we demonstrate the application of this system in 13C-labeling experiments.
{"title":"Carboxylations of (Hetero)Aromatic C–H Bonds Using an Alkyl Silyl Carbonate Reagent","authors":"Kanta Shimotai, Ozora Sasamoto, Masanori Shigeno","doi":"10.1021/acs.orglett.4c04388","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04388","url":null,"abstract":"In this paper, we report that the use of an alkyl silyl carbonate reagent combined with CsF and 18-crown-6 facilitates efficient direct carboxylations of (hetero)aromatic C–H bonds. This system also enables benzylic carboxylation of a toluene derivative and double carboxylation of methyl heteroarene. The carbonate reagent is characterized by its ease of handling and storage. Moreover, we demonstrate the application of this system in <sup>13</sup>C-labeling experiments.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"31 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142857681","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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