The Journal of Organic Chemistry最新文献

{"title":"Molecular Dynamics of the Davies Ambimodal C-H Functionalization/Cope Rearrangement Reaction.","authors":"Yaling Zhang, Chaoqin Cao, Yuanbin She, Huw M L Davies, Yun-Fang Yang, K N Houk","doi":"10.1021/acs.joc.4c01682","DOIUrl":"10.1021/acs.joc.4c01682","url":null,"abstract":"<p><p>The mechanism of the dirhodium-catalyzed combined C-H functionalization/Cope rearrangement (CH/Cope) reaction discovered by the Davies group has been investigated with density functional theory (DFT) calculations and quasi-classical molecular dynamics (MD) simulations. Computations from the Davies group previously showed that there is a post-transition state bifurcation leading to a direct CH reaction and also to the CH/Cope product. While this work was in preparation, the Tantillo group and the Ess group independently reported quantum mechanical and molecular dynamics studies on the dirhodium-tetracarboxylate-catalyzed diazoester CH/Cope and CH insertion reactions with 1,3-cyclohexadiene and 1,4-cyclohexadiene, respectively. The Tantillo group cited \"dynamic mismatching\" to explain the origins of the low yield of CH/Cope products in some experiments; the Ess group explained the origins of product selectivity from the perspective of TS vibrational modes and their synchronization that occurs at the entropic intermediates. We report quasi-classical trajectories for the reaction of the carbene with 1-methylcyclohexene that afford both the CH/Cope and C-H insertion products. After passing through the transition state that involves mostly hydrogen transfer, momentum drives the reaction trajectories toward the CH/Cope products.</p>","PeriodicalId":57,"journal":{"name":"The Journal of Organic Chemistry","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142666617","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":"Protecting Group Control of Hydroxyketone-Hemiketal Tautomeric Equilibrium Enables the Stereoselective Synthesis of a 1<i>'</i>-Azido <i>C</i>-Nucleoside.","authors":"Subhankar Panda, Moyosore O Orimoloye, Tej Narayan Poudel, Steven De Jonghe, Dirk Jochmans, Johan Neyts, Courtney C Aldrich","doi":"10.1021/acs.joc.4c01981","DOIUrl":"10.1021/acs.joc.4c01981","url":null,"abstract":"<p><p>The synthesis of 1<i>'</i>-azido <i>C</i>-nucleosides is described to expand the set of azide-functionalized nucleosides for bioorthogonal applications and as potential antiviral drugs. Lewis acid-promoted azidation of a nucleoside hemiketal resulted in the formation of a tetrazole through a Schmidt reaction manifold. Conformational control to prevent ring-chain tautomerism enabled efficient 1<i>'</i>-azidation with complete β-diastereoselectivity. The unique reactivity and further derivation of the 1<i>'</i>-azido <i>C</i>-nucleosides are also reported.</p>","PeriodicalId":57,"journal":{"name":"The Journal of Organic Chemistry","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142666620","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":"A Method for the Preparation of Fused Dinitromethyl High-Energy-Density Materials","authors":"Chengchuang Li, Teng Zhu, Luyao Chen, Caijin Lei, Jie Tang, Guangbin Cheng, Chuan Xiao, Hongwei Yang","doi":"10.1021/acs.joc.4c01699","DOIUrl":"https://doi.org/10.1021/acs.joc.4c01699","url":null,"abstract":"This work investigates a simple synthetic method for producing fused dinitromethyl energetic compounds. Fused compound <b>2</b> has a high detonation velocity (9358 m s^–1) close to that of the well-known high-energy-density explosive CL-20 (9455 m s^–1), an extremely high density (1.97 cm^–1), and acceptable sensitivity (IS = 8 J). The good thermal stability of <b>2</b> (<i>T</i>_d = 181 °C) is rarely reported in the field of dinitromethyl-based high explosives. The results show that compound <b>2</b> is a promising candidate for high explosives and provide new insight into the synthesis of dinitromethyl compounds.","PeriodicalId":57,"journal":{"name":"The Journal of Organic Chemistry","volume":"35 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673367","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":"Correction to “Chemical Bonding and Aromaticity in Furan, Pyrrole, and Thiophene: A Magnetic Shielding Study”","authors":"Kate E. Horner, Peter B. Karadakov","doi":"10.1021/acs.joc.4c02794","DOIUrl":"https://doi.org/10.1021/acs.joc.4c02794","url":null,"abstract":"The NICS(0), NICS(0.5), and NICS(1) values in our paper were taken from the data used to construct the isotropic shielding contour plots for furan, pyrrole, and thiophene shown in Figures 1–6, at the points with coordinates (0.0, 0.0, 0.0), (0.0, 0.0, 0.5), and (0.0, 0.0, 1.0) (in angstroms; the <i>x</i> and <i>y</i> coordinates are along the horizontal and vertical axes, respectively, in Figures 1a–3a). These points are shifted from the geometric ring centers along the respective <i>y</i> axes; to follow the convention for calculating NICS, separate NICS(0), NICS(0.5), and NICS(1) calculations should have been performed at the points with coordinates corresponding to the exact geometric ring centers, (0.0, −0.01277, 0.0), (0.0, −0.01277, 0.5), and (0.0, −0.01277, 1.0) for furan, (0.0, −0.03584, 0.0), (0.0, −0.03584, 0.5), and (0.0, −0.03584, 1.0) for pyrrole, and (0.0, −0.27121, 0.0), (0.0, −0.27121, 0.5), and (0.0, −0.27121, 1.0) for thiophene. The correct NICS(0), NICS(0.5), and NICS(1) values for the three molecules are shown in the corrected Table 1 (all nuclear shieldings remain unchanged). The changes to the NICS values for furan and pyrrole are relatively minor, but the changes to the NICS values for thiophene are more substantial. The correct HF-GIAO NICS(1), MP2-GIAO NICS(0.5), and MP2-GIAO NICS(1) values still indicate that thiophene is more aromatic than pyrrole, but the correct HF-GIAO NICS(0), HF-GIAO NICS(0.5), and MP2-GIAO NICS(0) values make the opposite suggestion. It is important to emphasize that the analysis of the behavior of the isotropic shielding in molecular space illustrated by the contour plots in Figures 1–6 that employs considerably more data than single-point NICS calculations strongly favors the aromaticity order thiophene &gt; pyrrole &gt; furan supported by experimental evidence. The authors thank Emiel Vanden Berghe (Ph.D. researcher in the group of Patrick Bultinck, University of Ghent, Ghent, Belgium) who carried out HF-GIAO NICS(0) and NICS(1) calculations at the geometries of furan, pyrrole, and thiophene used in the paper and informed us of discrepancies with the published results. C₁ is the carbon adjacent to heteroatom Z. This article has not yet been cited by other publications.","PeriodicalId":57,"journal":{"name":"The Journal of Organic Chemistry","volume":"18 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673368","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":"Cobalt-Catalyzed Intramolecular Enantioselective Reductive Heck Reaction toward the Synthesis of Chiral 3-Trifluoromethylated Oxindoles","authors":"Qiang Wang, Zi-Sheng Ruan, Hong-Peng Wang, Ren-Xiao Liang, Yuan-Yuan Hu, Yi-Xia Jia","doi":"10.1021/acs.joc.4c01488","DOIUrl":"https://doi.org/10.1021/acs.joc.4c01488","url":null,"abstract":"Herein, a cobalt-catalyzed intramolecular enantioselective reductive Heck reaction is disclosed. Starting from <i>N</i>-<i>ortho</i>-iodoaryl-2-(trifluoromethyl)acrylamides, a plethora of chiral oxindoles bearing trifluoromethylated quaternary stereogenic centers at the C3-position are achieved in moderate to good yields (up to 88% yield) and good to excellent enantioselectivities (up to 94% ee) by employing zinc/silane as reducing agent. Other than the trifluoromethyl group, a number of chiral oxindoles bearing alkyl, aryl, and ester groups at C3-position were also obtained albeit in relatively lower enantioselectivities (68–78% ee).","PeriodicalId":57,"journal":{"name":"The Journal of Organic Chemistry","volume":"13 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673366","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":"C2-Arylated Indoles and Benzofurans through Formal (4 + 1) Annulation of <i>N</i>-Sulfonyl-2-aminobenzaldehydes and Salicylaldehyde Derivatives with Electron-Deficient Benzyl Chlorides.","authors":"Lillian A de Ceuninck van Capelle, Kimia Rahmannia, James M Macdonald, Christopher Richardson, Michael G Gardiner, John H Ryan, Rasool Babaahmadi, Steven M Wales, Christopher J T Hyland","doi":"10.1021/acs.joc.4c02231","DOIUrl":"10.1021/acs.joc.4c02231","url":null,"abstract":"<p><p>A two-step formal (4 + 1) annulation-dehydration reaction offers a convenient route to C2-arylated indoles and benzofurans. This reaction exploits the bifunctional reactivity of electron-deficient benzyl chlorides with <i>N</i>-sulfonyl-2-aminobenzaldehydes or salicylaldehyde derivatives. The reaction tolerates both electron-withdrawing and donating groups on the substituted aldehydes, as well as variation of electron-withdrawing groups at the <i>para</i> position of the benzyl chloride reagent. This work also identifies interesting byproducts resulting from the self-reaction of these benzyl chlorides under basic conditions.</p>","PeriodicalId":57,"journal":{"name":"The Journal of Organic Chemistry","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142666504","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":"Synthesis of Sulfinamidines via Iron-Catalyzed Nitrene Transfer Reaction with Sulfenamides.","authors":"Zhi-Kun Zhang, Yin Yuan, Huiling Peng, Yidan Han, Junliang Zhang, Junfeng Yang","doi":"10.1021/acs.joc.4c02286","DOIUrl":"10.1021/acs.joc.4c02286","url":null,"abstract":"<p><p>An iron-catalyzed nitrene transfer reaction for the rapid synthesis of sulfinamidines from readily available sulfenamides is reported. This method features mild conditions, short reaction times, and a broad substrate scope, allowing the preparation of a variety of sulfinamidines in good to excellent yields. The synthetic utility of the sulfinamidine products was further demonstrated through their conversion to other valuable sulfur(VI) compounds, such as sulfondiimidoyl fluorides, sulfinamidiate esters, and sulfonimidamides. Preliminary efforts in the development of an asymmetric variant showed moderate enantioselectivity.</p>","PeriodicalId":57,"journal":{"name":"The Journal of Organic Chemistry","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142666622","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":"Cobalt-Catalyzed Regioselective C8-H Sulfoxamination of 1-Naphthylamine Derivatives with NH-Sulfoximines.","authors":"Nileshkumar B Rathod, Raj N Patel, Sachinkumar D Patel, Dharmik M Patel, Mahesh A Sonawane, Dinesh Gopichand Thakur, Subhash Chandra Ghosh","doi":"10.1021/acs.joc.4c02318","DOIUrl":"10.1021/acs.joc.4c02318","url":null,"abstract":"<p><p>A simple cobalt-catalyzed, picolinamide-directed C8-H sulfoxamination of 1-naphthalamides with NH-sulfoximines has been developed. This cross-dehydrogenative C-H/N-H coupling reaction offers a facile route to N-arylated sulfoximines, exhibiting high yields, a broad substrate scope, and excellent functional group tolerance and scalability.</p>","PeriodicalId":57,"journal":{"name":"The Journal of Organic Chemistry","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142666506","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":"Development of a Highly Enantioselective Catalytic Di-π-methane Rearrangement.","authors":"Samuel B Cahoon, Steven J Chapman, Tahoe A Fiala, Matthew J Genzink, Tehshik P Yoon","doi":"10.1021/acs.joc.4c02383","DOIUrl":"https://doi.org/10.1021/acs.joc.4c02383","url":null,"abstract":"<p><p>The di-π-methane (DPM) rearrangement is an important organic photorearrangement that converts 1,4-diene-containing compounds to vinyl cyclopropanes, often resulting in extensive, synthetically valuable restructuring of the substrate's carbon framework. We investigated the influence of Lewis and Brønsted acids on the DPM rearrangement of dibenzobarrelenes. These studies have culminated in the identification of a dual chiral Brønsted acid-iridium photosensitizer system that enables the first highly enantioselective catalytic all-carbon DPM rearrangement.</p>","PeriodicalId":57,"journal":{"name":"The Journal of Organic Chemistry","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142646524","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":"Robust Organocatalytic Three-Component Approach to 1,3-Diarylallylidene Pyrazolones via Consecutive Double Condensation Reactions","authors":"Ashvani K. Patel, Sampak Samanta","doi":"10.1021/acs.joc.4c02273","DOIUrl":"https://doi.org/10.1021/acs.joc.4c02273","url":null,"abstract":"A robust pyrrolidine-BzOH salt-catalyzed one-pot three-component reaction involving 4-unsubstituted pyrazolones, aryl/heteroarylaldehydes, and aryl methyl ketones is reported for the first time. This catalytic process fortifies an efficient method, allowing for the practical synthesis of a wide array of synthetically useful 1,3-diarylallylidene pyrazolones in good to high yields exclusively in their single geometrical isomer forms. Furthermore, this catalyst facilitates a sequential double condensation reaction under thermal conditions, thereby enabling two consecutive C═C bonds through displacement of aryl groups. Moreover, this organocatalytic technique achieves a 100% carbon atom economy, marking a significant step forward toward efficient and sustainable synthesis.","PeriodicalId":57,"journal":{"name":"The Journal of Organic Chemistry","volume":"62 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642974","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}