Organic LettersPub Date : 2024-12-18DOI: 10.1021/acs.orglett.4c04484
Lin Tian, Pu Chen, Xiaochen Ji, Guo-Jun Deng, Huawen Huang
{"title":"Photoredox Radical Truce–Smiles Rearrangement of N-Sulfinyl Acrylamides with Bromodifluoroacetamides","authors":"Lin Tian, Pu Chen, Xiaochen Ji, Guo-Jun Deng, Huawen Huang","doi":"10.1021/acs.orglett.4c04484","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04484","url":null,"abstract":"We herein report a photochemical Truce–Smiles rearrangement reaction of <i>N</i>-sulfinyl acrylamides with bromodifluoroacetamides resulting in the synthesis of a series of aryl difluoroglutaramides in moderate to good yields. The asymmetric synthesis using chiral sulfinamides produced quaternary carbon<i>-</i>centered glutaramide products with a modest enantioselectivity. This protocol effectively complements previous Truce–Smiles rearrangement methods involving <i>N</i>-sulfonyl acrylamides.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"23 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841822","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}
{"title":"Photocatalytic Generation of β-Fluoroalkylated α-Carbonyl Carbocations","authors":"Chong-Jin Zhang, Zhen-Zhen Liu, Yan-Biao Kang, Jian-Ping Qu","doi":"10.1021/acs.orglett.4c04273","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04273","url":null,"abstract":"Nucleophilic addition to α,β-unsaturated carbonyl compounds normally occurs at the carbonyl carbon or β-carbon. The direct α-nucleophilic addition at the α-carbon can hardly be achieved due to electronic mismatch. In this work, we report the nucleophilic addition of β-fluoroalkyl α-carbonyl carbocations that are prepared via <b>CBZ6</b>-induced redox-neutral photocatalysis. In this process, the photocatalytic oxidation of the β-fluoroalkyl α-carbonyl radical to the corresponding carbocation is the key step. The β-fluoroalkyl α-carbonyl radical is generated in situ by the addition of a polyfluoroalkyl radical, which is generated by the photocatalytic fragmentation of polyfluoroalkyl sulfonyl chloride, to α,β-unsaturated carbonyls. The high <i>E</i><sub>00</sub> value of <b>CBZ6</b> (3.19 V vs the saturated calomel electrode), which corresponds with the absorbed photoenergy, contributes to the high catalytic reactivity.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"64 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849699","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}
{"title":"Asymmetric Total Synthesis of (+)-Hyperbeanol A","authors":"Xingchao Guan, Haodong Wang, Wanqiao Zhang, Zhixiang Xie","doi":"10.1021/acs.orglett.4c02930","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c02930","url":null,"abstract":"A bioinspired alkylation dearomatization reaction was developed to construct the 5/6/6 fused-spiro tricyclic core framework and spiro-quaternary carbon chiral center. The usage of this approach for assembling these natural products of spirocyclic polycyclic polyprenylated acylphloroglucinols with an octahydrospiro-[cyclohexan-1,5′-indene] core is demonstrated by the first asymmetric total synthesis of highly oxidized hyperbeanol A.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"20 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849835","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}
Organic LettersPub Date : 2024-12-17DOI: 10.1021/acs.orglett.4c04196
Ganesh H. Shinde, Hugo Castlind, Ganesh S. Ghotekar, Francoise M. Amombo Noa, Lars Öhrström, Henrik Sundén
{"title":"Site Selective Boron Directed Ortho Benzylation of N-Aryl Amides: Access to Structurally Diversified Dibenzoazepines","authors":"Ganesh H. Shinde, Hugo Castlind, Ganesh S. Ghotekar, Francoise M. Amombo Noa, Lars Öhrström, Henrik Sundén","doi":"10.1021/acs.orglett.4c04196","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04196","url":null,"abstract":"We present a highly selective protocol for the <i>ortho</i> benzylation of <i>N</i>-aryl amides. This method offers mild conditions, excellent site specificity, and scalability, enabling the synthesis of diarylmethane amides and dibenzoazepines. The protocol allows for one-pot diagonal dibenzylation of dianilides, creating valuable precursors for pharmaceutically active compounds and addressing limitations in current direct C–H activation methodologies.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"23 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841753","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}
Organic LettersPub Date : 2024-12-17DOI: 10.1021/acs.orglett.4c04379
Camille Tisnerat, Samuele Di Ciano, Fabrizio Pertusati, Michaela Serpi
{"title":"Microwave-Accelerated Synthesis of Novel Triphosphate Nucleoside Prodrugs: Expanding the Therapeutic Arsenal of Anticancer Agents","authors":"Camille Tisnerat, Samuele Di Ciano, Fabrizio Pertusati, Michaela Serpi","doi":"10.1021/acs.orglett.4c04379","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04379","url":null,"abstract":"In this study, we report for the first time a microwave-accelerated synthesis of purine and pyrimidine nucleoside triphosphate prodrugs, whose γ phosphate is masked with an aryloxy moiety and an amino acid ester (γ-ProTriP). The synthetic utility of this method is illustrated by the synthesis of triphosphate prodrugs of clofarabine and gemcitabine, two FDA-approved anticancer drugs. These new prodrugs showed good chemical and rat serum stability. Remarkably the clofarabine prodrug showed significant cytotoxicity against a panel of cancer cell lines.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"24 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841824","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}
Organic LettersPub Date : 2024-12-17DOI: 10.1021/acs.orglett.4c04453
Ying Huang, You-Feng Han, Chun-Lin Zhang, Song Ye
{"title":"Regioselective Alkylacylation of 1,3-Dienes by Merging N-Heterocyclic Carbene Catalysis with Photoinduced Palladium Catalysis","authors":"Ying Huang, You-Feng Han, Chun-Lin Zhang, Song Ye","doi":"10.1021/acs.orglett.4c04453","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04453","url":null,"abstract":"Herein, we develop a dual catalytic platform for the 1,2- or 1,4-alkylacylation reaction of 1,3-dienes with readily available alkyl halides and aldehydes by merging <i>N</i>-heterocyclic carbene catalysis with photoinduced palladium catalysis. A series of β,γ-unsaturated ketones are obtained in good to high yields. Mechanistic studies suggest that this reaction involves a radical process. The direct synthesis of flavanone from salicylaldehyde exemplified the potential capability of this dual catalytic platform.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"12 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841826","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}
{"title":"Programmable Synthesis of Cationic Azaperylenes via Rh(III)-Catalyzed Multiple C–H/N–H Bonds Activation and Annulation","authors":"Hui Li, Yiling Zeng, Fangpeng Liang, Yanyan Yang, Kaida Li, Futao Pang, Shiqing Li","doi":"10.1021/acs.orglett.4c04269","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04269","url":null,"abstract":"Rh(III)-catalyzed dual N–H and triple C–H activation/(4 + 2) annulation of 2-aryl-2,3-dihydro-1<i>H</i>-perimidines and alkynes has been disclosed to construct 4,5,14,15-tetrasubstituted cationic azaperylenes with high yields (up to 95%) and broad scope. Tandem (4 + 2) annulation of 1<i>H</i>-perimidines with vinylene carbonate and alkynes affords 4,5-disubstituted azaperylene salts, and <i>ortho</i>-alkynyl 1<i>H</i>-perimidines undergo an intra- and intermolecular annulation cascade to give 4,5,14-trisubstituted targets. Most of the intermediates were detected by ESI-MS, indicating a convincible mechanism including three possible paths. The resultant new cationic azaperylenes generally exhibit yellow to red emissions (540–642 nm), and the disubstituted cations exhibit longer emission wavelengths than their tri- and tetra-substituted partners. This protocol also offers a concise and efficient tool to construct perimidinium-based dications, showing potential applications in electrochromic devices.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"23 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142833010","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}
Organic LettersPub Date : 2024-12-17DOI: 10.1021/acs.orglett.4c04160
Sanaz Rajabalinia, Hedieh Lotfian, Sabrina Hoford, Muyuan Wang, Maxime A. Siegler, Thomas Lectka, Travis Dudding
{"title":"FON: An Innovative Fluorinated Group via Hydroetherification-Type Reactivity","authors":"Sanaz Rajabalinia, Hedieh Lotfian, Sabrina Hoford, Muyuan Wang, Maxime A. Siegler, Thomas Lectka, Travis Dudding","doi":"10.1021/acs.orglett.4c04160","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04160","url":null,"abstract":"An efficient strategy for preparing the novel <i>O</i>-difluoroalkylhydroxylamine fluorinated functional group, coined FON, is reported. This analogue of medicinally important β-phenethyl ether scaffolds in uniting <i>gem</i>-difluoro and N–O moieties is synthesized in one step via chemo- and regioselectivity metal-free hydroetherification-type additions. As shown, this unique mode of reactivity is realized for a diverse substrate scope and applied to gram-scale synthesis and site-selective deuterium incorporation. Lastly, a mechanistic understanding with implications in Brønsted acid catalysis is offered.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"51 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841823","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}
Organic LettersPub Date : 2024-12-17DOI: 10.1021/acs.orglett.4c04171
Patrick Daley-Dee, James Clarke, Sebastien Monfette, Robin B. Bedford
{"title":"Iron-Catalyzed Miyaura Borylation of Aryl Chlorides and Triflates","authors":"Patrick Daley-Dee, James Clarke, Sebastien Monfette, Robin B. Bedford","doi":"10.1021/acs.orglett.4c04171","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04171","url":null,"abstract":"Simple aryl chlorides represent challenging substrates in iron-catalyzed borylation. A combination of Li[B(<sup>t</sup>Bu)pin-Bpin] as the borylating reagent and a catalyst formed in situ from iron(II) triflate and the commercially available N-heterocyclic carbene ligand, IMes, gives significantly improved activity and a much broader scope than previously reported iron-based catalysts. Iron triflate is also a good precatalyst for the borylation of aryl triflates─a previously unreported transformation─and in these cases the IMes ligand is not required.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"52 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841926","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}
{"title":"Rational Synthesis of Highly Stable Dithienopyrrole-Embedded BODIPYs Exhibiting Large Stokes Shift","authors":"Gayathri Krishnan, Aathira Edwin, Muniappan Kalipriyadharshini, Achsah Anna, Shanmugam Easwaramoorthi, Sabapathi Gokulnath","doi":"10.1021/acs.orglett.4c04329","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c04329","url":null,"abstract":"A series of dithienopyrrole (DTP) embedded BODIPYs were synthesized and structurally characterized. These BODIPYs have strong absorption in the green region and broad emission in the red region with a large Stokes shift ranging from 3100 to 4200 cm<sup>–1</sup>. Interestingly, all three BODIPYs show intramolecular charge transfer interaction (ICT). Intriguingly, both BODIPYs (<i>bis</i>- and <i>tris</i><b>-BOD</b>) also exhibit excited state symmetry breaking (ES-SB). Single-crystal X-ray analysis unambiguously confirmed the exact structures of all three structurally distinct BODIPYs.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"20 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142833012","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}