Journal of Organic Chemistry最新文献

{"title":"Rhodium-Catalyzed Aromatic C-H Allylation with α,β-Unsaturated Imines.","authors":"Wei-Tao Hu,Zhong-Xia Wang","doi":"10.1021/acs.joc.5c00484","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00484","url":null,"abstract":"Reaction of 2-arylpyridines with α,β-unsaturated imines in the presence of 2.5 mol % of [Cp*RhCl2]2 and 10 mol % of AgSbF6 in acetone affords allylated 2-arylpyridines with an enamine unit located in the allyl segment. This method features ortho-monoallylation selectivity and Z-selectivity of the C-C double bonds, is applicable to a wide range of substrates, and is compatible with air and functional groups such as halides, CF3, COOMe, OH, MeO, and ketal groups.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"113 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143945343","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}

{"title":"Rhodium-Catalyzed Aromatic C–H Allylation with α,β-Unsaturated Imines","authors":"Wei-Tao Hu,&nbsp; and ,&nbsp;Zhong-Xia Wang*,&nbsp;","doi":"10.1021/acs.joc.5c0048410.1021/acs.joc.5c00484","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00484https://doi.org/10.1021/acs.joc.5c00484","url":null,"abstract":"<p >Reaction of 2-arylpyridines with α,β-unsaturated imines in the presence of 2.5 mol % of [Cp*RhCl₂]₂ and 10 mol % of AgSbF₆ in acetone affords allylated 2-arylpyridines with an enamine unit located in the allyl segment. This method features <i>ortho</i>-monoallylation selectivity and <i>Z</i>-selectivity of the C–C double bonds, is applicable to a wide range of substrates, and is compatible with air and functional groups such as halides, CF₃, COOMe, OH, MeO, and ketal groups.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 20","pages":"6755–6767 6755–6767"},"PeriodicalIF":3.3,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144114753","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}

{"title":"Fluorescence Emissive Fluorinated Pyrimido[5,4-h]quinazolines: Synthesis, Structure, and Photophysical and Halochromic Properties.","authors":"Kirti Yadav,Taro Udagawa,Yasuhiro Kubota,Toshiyasu Inuzuka,Govindarajan Krishnamoorthy,Kazumasa Funabiki","doi":"10.1021/acs.joc.5c00506","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00506","url":null,"abstract":"Planar tricyclic aromatics and azaheteroaromatics are of significant interest to organic chemists in the field of materials science owing to their excellent photoconductivity, electroluminescence and fluorescence properties enabled by their rigid extended π-conjugation. Furthermore, tricyclic azaheteroaromatics are effective ligands for organometallic catalysis and a prominent drug discovery framework. Herein, we present the first one-step synthesis of a less-accessible tricyclic fluorophore comprising a 5,6-difluoro-2,9-diarylpyrimido[5,4-h]quinazoline core entailing the regiospecific tandem condensation of tetrafluoroterephthalonitrile and derivatives of benzamidine hydrochloride in the presence of potassium carbonate or cesium carbonate under mild conditions. Single-crystal X-ray diffractometry studies confirmed the structure of the 5,6-difluoro-2,9-diarylpyrimido[5,4-h]quinazolines, and various interactions such as π-π stacking. Spectroscopic measurements, including ultraviolet-visible (UV-vis) and fluorescence spectroscopy, of the synthesized pyrimido[5,4-h]quinazolines revealed that they have excellent fluorescence properties both in the solution and solid states, displaying red-shifted maximum fluorescence wavelengths in the solid state compared to those in the solution state. Density functional theory (DFT) calculations and electrochemical analyses revealed that the introduction of an electron-withdrawing group, such as a halogen, stabilized the energy levels. Thermogravimetric (TG) analysis indicated high decomposition temperatures for 5,6-difluoro-2,9-diarylpyrimido[5,4-h]quinazolines, confirming their favorable thermal stability. Finally, the halochromism of 5,6-difluoro-2,9-diarylpyrimido[5,4-h]quinazolines arising from the protonation of the amino group and/or pyrimidine backbone is described.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"121 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143945344","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}

{"title":"Photoinduced Regio- and Stereoselective Hydrotrifluoromethylation of Glycals with Langlois Reagent.","authors":"Tian Li,Miao Liu,Zhao-Xiang Luo,Xian-Jin Qin,Xin-Shan Ye,De-Cai Xiong","doi":"10.1021/acs.joc.5c00193","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00193","url":null,"abstract":"Fluorination has demonstrated the potential to improve the physicochemical and enzymatic properties of carbohydrates. Hydrotrifluoromethylation is an emerging reaction to introduce trifluoromethyl groups. However, the hydrotrifluoromethylation of glycals has been challenging because of the lack of regioselectivity and stereoselectivity. Herein, we describe an efficient, highly selective, and broadly applicable photoinduced hydrotrifluoromethylation strategy of glycals using cost-effective sodium trifluoromethanesulfonate to give 1,2-dideoxy-2-trifluoromethyl sugars.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"4 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143945104","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}

{"title":"Fluorescence Emissive Fluorinated Pyrimido[5,4-h]quinazolines: Synthesis, Structure, and Photophysical and Halochromic Properties","authors":"Kirti Yadav,&nbsp;Taro Udagawa,&nbsp;Yasuhiro Kubota,&nbsp;Toshiyasu Inuzuka,&nbsp;Govindarajan Krishnamoorthy and Kazumasa Funabiki*,&nbsp;","doi":"10.1021/acs.joc.5c0050610.1021/acs.joc.5c00506","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00506https://doi.org/10.1021/acs.joc.5c00506","url":null,"abstract":"<p >Planar tricyclic aromatics and azaheteroaromatics are of significant interest to organic chemists in the field of materials science owing to their excellent photoconductivity, electroluminescence and fluorescence properties enabled by their rigid extended π-conjugation. Furthermore, tricyclic azaheteroaromatics are effective ligands for organometallic catalysis and a prominent drug discovery framework. Herein, we present the first one-step synthesis of a less-accessible tricyclic fluorophore comprising a 5,6-difluoro-2,9-diarylpyrimido[5,4-<i>h</i>]quinazoline core entailing the regiospecific tandem condensation of tetrafluoroterephthalonitrile and derivatives of benzamidine hydrochloride in the presence of potassium carbonate or cesium carbonate under mild conditions. Single-crystal X-ray diffractometry studies confirmed the structure of the 5,6-difluoro-2,9-diarylpyrimido[5,4-<i>h</i>]quinazolines, and various interactions such as π–π stacking. Spectroscopic measurements, including ultraviolet–visible (UV–vis) and fluorescence spectroscopy, of the synthesized pyrimido[5,4-<i>h</i>]quinazolines revealed that they have excellent fluorescence properties both in the solution and solid states, displaying red-shifted maximum fluorescence wavelengths in the solid state compared to those in the solution state. Density functional theory (DFT) calculations and electrochemical analyses revealed that the introduction of an electron-withdrawing group, such as a halogen, stabilized the energy levels. Thermogravimetric (TG) analysis indicated high decomposition temperatures for 5,6-difluoro-2,9-diarylpyrimido[5,4-<i>h</i>]quinazolines, confirming their favorable thermal stability. Finally, the halochromism of 5,6-difluoro-2,9-diarylpyrimido[5,4-<i>h</i>]quinazolines arising from the protonation of the amino group and/or pyrimidine backbone is described.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 20","pages":"6789–6803 6789–6803"},"PeriodicalIF":3.3,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144114712","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}

{"title":"Central-to-Axial-to-Central Chirality Transfer in the Au(I)-Catalyzed Cycloisomerization of Propargyl Vinyl Ethers to Cyclopentadienes","authors":"Dina Scarpi,&nbsp;Giovanni Turchi,&nbsp;Matteo Fazzini,&nbsp;Lucilla Favero and Ernesto G. Occhiato*,&nbsp;","doi":"10.1021/acs.joc.5c0043310.1021/acs.joc.5c00433","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00433https://doi.org/10.1021/acs.joc.5c00433","url":null,"abstract":"<p >An easy approach to the enantioselective synthesis of five-, six-, and seven-membered ring-fused cyclopentadienes (85–99% ee) is based on the Au(I)-catalyzed cycloisomerization of enantiomerically pure or enriched propargyl vinyl ethers, which occurs with complete central-to-axial-to-central chirality transfer. DFT calculations show that the formation of a nonplanar σ-Au(I)-pentadienyl cation intermediate having a helical configuration, which quickly cyclizes to form the target cyclopentadiene, accounts for the lack of erosion of the initial optical purity. From a synthetic point of view, when the cyclopentadienes are subjected to a quick 1,5-<i>H</i> shift and cannot be isolated as pure regioisomers, they can be trapped <i>in situ</i> by suitable dienophiles during or immediately after the gold(I)-catalyzed cycloisomerization to form more complex polycyclic compounds. The synthesis of an enantiomerically pure α-tertiary amine was realized to demonstrate the usefulness of this approach.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 20","pages":"6743–6754 6743–6754"},"PeriodicalIF":3.3,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.joc.5c00433","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144114784","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Construction of C–S and C–Se Bonds via Photocatalytic Aromatization-Driven Deconstructive Diversification of Spiro-Dihydroquinazolinones Derived from Unstrained Ketones","authors":"Tao Wang,&nbsp;Jin-Long Dai,&nbsp;Yi-Feng Jiang,&nbsp;Shenghu Yan* and Jia-Yin Wang*,&nbsp;","doi":"10.1021/acs.joc.5c0049910.1021/acs.joc.5c00499","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00499https://doi.org/10.1021/acs.joc.5c00499","url":null,"abstract":"<p >A novel and robust deconstructive functionalization reaction of spiro-dihydroquinazolinones with sulfenylating reagents in the presence of base has been realized under visible light irradiation. This reaction enabled the direct ring-opening of unstrained cyclic ring systems, producing skeletally diverse functionalized quinazolinones with moderate to good yields. A range variety of sulfenylating reagents including diaryl disulfide, thiosulfonate, dithiosulfonate and 1-[(trifluoromethyl)thio]-2,5-pyrrolidinedione were compatible for this transformation. In addition, diaryl diselenide and selenosulfonate could also couple with <i>spiro</i>-dihydroquinazolinones to form C–Se Bonds. Mechanistic studies revealed that the reaction proceeds via a radical–radical coupling pathway.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 20","pages":"6776–6788 6776–6788"},"PeriodicalIF":3.3,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144114789","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}

{"title":"Visual Detection of Cumulative Exposure to Amines by Controlling the Fate of the Excited State of Photochromic Dithienylethenes","authors":"Nazanin Assempour,&nbsp;Farahnaz Nourmohammadian,&nbsp;Brahmjot Kaur,&nbsp;Rameez Raza and Neil R. Branda*,&nbsp;","doi":"10.1021/acs.joc.5c0033110.1021/acs.joc.5c00331","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00331https://doi.org/10.1021/acs.joc.5c00331","url":null,"abstract":"<p >A convenient, visual detection system for environmental monitoring of amines and acyl-transfer reactions is based on the fate of the excited state of photoresponsive dithienylethene derivatives, where the disappearance of color provides a measure of the extent of acyl transfer and, therefore, the amount of amine present.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 20","pages":"6737–6742 6737–6742"},"PeriodicalIF":3.3,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144114924","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}

{"title":"Photoinduced [3 + 2] Radical Cyclization of α-Diazodifluoroethyl Sulfonium Salt with Hydrazones","authors":"Ming-Yue He,&nbsp;Hao-Yan Wu,&nbsp;Xiaodong Tang,&nbsp;Jun-An Ma and Fa-Guang Zhang*,&nbsp;","doi":"10.1021/acs.joc.5c0067510.1021/acs.joc.5c00675","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00675https://doi.org/10.1021/acs.joc.5c00675","url":null,"abstract":"<p >Here we report a photoinduced [3 + 2] radical cyclization reaction of α-diazodifluoroethane sulfonium reagent with hydrazones to give the corresponding <i>N</i>-amino-4-difluoromethyl-1,2,3-triazoles. This transformation proceeds under simple blue light irradiation conditions without the need of photocatalyst. Preliminary mechanistic studies indicate that the formation of an electron donor–acceptor (EDA) complex between electron-deficient α-diazo sulfonium triflate and electron-rich hydrazone operates as the key mediator.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 20","pages":"6834–6843 6834–6843"},"PeriodicalIF":3.3,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144114641","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}

{"title":"Formation of 2,3-Dihydrofurans via Bifunctional Biphenyl-2-ylphosphine Ligand Enables Gold-Catalyzed Cyclo-Isomerization of But-2-yn-1-ols or α-Allenols","authors":"Xiaoni Jia,&nbsp;Yuanmeng Kan,&nbsp;Wenguang Li,&nbsp;Weiguang Kong,&nbsp;Jian Wang,&nbsp;Ming Chen* and Ting Li*,&nbsp;","doi":"10.1021/acs.joc.5c0080110.1021/acs.joc.5c00801","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00801https://doi.org/10.1021/acs.joc.5c00801","url":null,"abstract":"<p >In this work, we report a gold-catalyzed intramolecular cyclo-isomerization of but-2-yn-1-ols for the construction of 2,3-dihydrofurans under mild reaction conditions. The gold catalysis is enabled by a bifunctional phosphine ligand, and the reaction tolerates a range of substituents and exhibits good efficiencies.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 20","pages":"6854–6861 6854–6861"},"PeriodicalIF":3.3,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144114921","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}