Organic Letters最新文献

{"title":"Palladium-Catalyzed Carbonylative Cyclization of 1-Alkynyl-2-iodo-d-glucal.","authors":"Milene M Hornink, Giuseppe E Figlino, Mônica F Z J Toledo, Daniel C Pimenta, Hélio A Stefani","doi":"10.1021/acs.orglett.4c03337","DOIUrl":"10.1021/acs.orglett.4c03337","url":null,"abstract":"<p><p>Cascade reactions are important synthetic tools for the synthesis of heterocyclic molecules, particularly those catalyzed by palladium. Herein, we report a palladium-catalyzed aminocarbonylative cyclization of new 1-alkynyl-2-iodo-d-glucals, which undergo a tandem carbonylative cyclization in the presence of various amine nucleophiles. A broad range of aromatic and aliphatic amines were applied as coupling partners, resulting in the selective and high-yield synthesis of glycosides fused to pyridinones. A plausible mechanism is proposed, proceeding via a tandem palladium aminocarbonylation followed by a palladium-catalyzed <i>endo-dig</i> cyclization.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":null,"pages":null},"PeriodicalIF":4.9,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11474949/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142337310","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis, Structure, and Redox Properties of Nonsymmetric 6-Oxoverdazyls","authors":"Nagalexmi Mamveedu Saji, Madeleine R. Taylor, Daniel M. Mazzucato, Paul J. Low, Li Feng Lim, Nicholas Cox, Nicholas F. Chilton, Stephen A. Moggach, Gemma F. Turner, Marcus J. Giansiracusa, Colette Boskovic, Curtis C. Ho, Stuart C. Thickett, Melissa K. Stanfield, Alex C. Bissember, Rebecca O. Fuller","doi":"10.1021/acs.orglett.4c02854","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c02854","url":null,"abstract":"Nonsymmetric 6π-electron (“oxidized”) 6-oxoverdazyls have been synthesized for the first time. After formal incorporation of a hydrogen atom, the corresponding 7π-electron neutral verdazyl radical is generated. The 7π radical can undergo a further electrochemically reversible reduction to an 8π anion. Both redox processes occur at more moderate potentials than the parent verdazyl, tuning the accessible potential windows of 6π, 7π, and 8π verdazyl species.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":null,"pages":null},"PeriodicalIF":5.2,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398345","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":"An Enantioselective Decarboxylative Glycolate Aldol Reaction","authors":"Md. Ataur Rahman, Mohammad Rehan, Torsten Cellnik, Brij Bhushan Ahuja, Alan R. Healy","doi":"10.1021/acs.orglett.4c03251","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c03251","url":null,"abstract":"Herein, we report the application of a benzyloxy-functionalized malonic acid half thioester as an activated ester equivalent in a highly enantioselective decarboxylative glycolate aldol reaction. This robust method operates at ambient temperature, tolerates air and moisture, and generates CO₂ as the only byproduct. The synthetic applicability of the method is demonstrated by the large-scale enantiodivergent synthesis of α-benzyloxy-β-hydroxybutyric acid thioester and its subsequent conversion to diverse polyoxygenated building blocks, deoxy-sugars, and (−)-angiopterlactone B.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":null,"pages":null},"PeriodicalIF":5.2,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398352","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":"Correction to “Regioselective Hydroboration of Unsymmetrical Internal Alkynes Catalyzed by a Cobalt Pincer-NHC Complex”","authors":"Naresh Kumar Meher, Maruti Suryavansi, K. Geetharani","doi":"10.1021/acs.orglett.4c03679","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c03679","url":null,"abstract":"We were made aware of an additional early discovery reported by Petit and co-workers on the cis-α-addition strategy for aryl-alkyl alkynes, which employed a phosphine-based ligand-substituted Cobalt-hydride catalyst. Thus, reference 10 in the original paper should be read as follows. (10) (a) &lt;contrib-group person-group-type=\"allauthors\"&gt;&lt;span&gt;Ferrand, L.&lt;/span&gt;; &lt;span&gt;Lyu, Y.&lt;/span&gt;; &lt;span&gt;Rivera-Hernández, A.&lt;/span&gt;; &lt;span&gt;Fallon, B. J.&lt;/span&gt;; &lt;span&gt;Amatore, M.&lt;/span&gt;; &lt;span&gt;Aubert, C.&lt;/span&gt;; &lt;span&gt;Petit, M.&lt;/span&gt;&lt;/contrib-group&gt; Hydroboration and Diboration of Internal Alkynes Catalyzed by a Well-Defined Low-Valent Cobalt Catalyst. &lt;cite&gt;&lt;i&gt;Synthesis&lt;/i&gt;&lt;/cite&gt; &lt;span&gt;2017&lt;/span&gt;, &lt;em&gt;49&lt;/em&gt;, 3895–3904.10.1055/s-0036-1588996&lt;/pub-id&gt;. (b) &lt;contrib-group person-group-type=\"allauthors\"&gt;&lt;span&gt;Obligacion, J. V.&lt;/span&gt;; &lt;span&gt;Neely, J. M.&lt;/span&gt;; &lt;span&gt;Yazdani, A. N.&lt;/span&gt;; &lt;span&gt;Pappas, I.&lt;/span&gt;; &lt;span&gt;Chirik, P. J.&lt;/span&gt;&lt;/contrib-group&gt; Cobalt Catalyzed Z-Selective Hydroboration of Terminal Alkynes and Elucidation of the Origin of Selectivity. &lt;cite&gt;&lt;i&gt;J. Am. Chem. Soc.&lt;/i&gt;&lt;/cite&gt;, &lt;span&gt;2015&lt;/span&gt;, &lt;em&gt;137&lt;/em&gt;, 5855–5858.10.1021/jacs.5b00936&lt;/pub-id&gt; (c) &lt;contrib-group person-group-type=\"allauthors\"&gt;&lt;span&gt;Ben-Daat, H.&lt;/span&gt;; &lt;span&gt;Rock, C. L.&lt;/span&gt;; &lt;span&gt;Flores, M.&lt;/span&gt;; &lt;span&gt;Groy, T. L.&lt;/span&gt;; &lt;span&gt;Bowman, A. C.&lt;/span&gt;; &lt;span&gt;Trovitch, R. J.&lt;/span&gt;&lt;/contrib-group&gt; Hydroboration of alkynes and nitriles using an α-diimine cobalt hydride catalyst. &lt;cite&gt;&lt;i&gt;Chem. Commun.&lt;/i&gt;&lt;/cite&gt; &lt;span&gt;2017&lt;/span&gt;, &lt;em&gt;53&lt;/em&gt;, 7333–7336.10.1039/C7CC02281F&lt;/pub-id&gt; (d) &lt;contrib-group person-group-type=\"allauthors\"&gt;&lt;span&gt;Zhang, G.&lt;/span&gt;; &lt;span&gt;Wu, S.&lt;/span&gt;; &lt;span&gt;Li, J.&lt;/span&gt;; &lt;span&gt;Zeng, H.&lt;/span&gt;; &lt;span&gt;Mo, Z.&lt;/span&gt;; &lt;span&gt;Davis, K.&lt;/span&gt;; &lt;span&gt;Zheng, S.&lt;/span&gt;&lt;/contrib-group&gt; Highly efficient and selective hydroboration of terminal and internal alkynes catalysed by a cobalt(II) coordination polymer. &lt;cite&gt;&lt;i&gt;Org. Chem. Front.&lt;/i&gt;&lt;/cite&gt; &lt;span&gt;2019&lt;/span&gt;, &lt;em&gt;6&lt;/em&gt;, 3228–3233.10.1039/C9QO00834A&lt;/pub-id&gt; (e) &lt;contrib-group person-group-type=\"allauthors\"&gt;&lt;span&gt;González, M. J.&lt;/span&gt;; &lt;span&gt;Bauer, F.&lt;/span&gt;; &lt;span&gt;Breit, B.&lt;/span&gt;&lt;/contrib-group&gt; Cobalt-Catalyzed Hydroboration of Terminal and Internal Alkynes. &lt;cite&gt;&lt;i&gt;Org. Lett.&lt;/i&gt;&lt;/cite&gt; &lt;span&gt;2021&lt;/span&gt;, &lt;em&gt;23&lt;/em&gt;, 8199–8203.10.1021/acs.orglett.1c02854&lt;/pub-id&gt; (f) &lt;contrib-group person-group-type=\"allauthors\"&gt;&lt;span&gt;Blasius, C. K.&lt;/span&gt;; &lt;span&gt;Vasilenko, V.&lt;/span&gt;; &lt;span&gt;Matveeva, R.&lt;/span&gt;; &lt;span&gt;Wadepohl, H.&lt;/span&gt;; &lt;span&gt;Gade, L. H.&lt;/span&gt;&lt;/contrib-group&gt; Reaction Pathways and Redox States in α-Selective Cobalt-Catalyzed Hydroborations of Alkynes. &lt;cite&gt;&lt;i&gt;Angew. Chem., Int. Ed.&lt;/i&gt;&lt;/cite&gt; &lt;span&gt;2020&lt;/span&gt;, &lt;em&gt;59&lt;/em&gt;, 23010–23014.10.1002/anie.202009625&lt;/pub-id&gt; (g) &lt;contrib-group person-group-type=\"allauthors\"&gt;&lt;span&gt;Bories, C. C.&lt;/span&gt;; &lt;span&gt;Sodreau, A.&lt;/span&gt;; &lt;span&gt;Barbazanges, M.&lt;/span&gt;; &lt;span&gt;Petit, M.&lt;/span&gt;&lt;/contrib-group&gt; Well-Defined Low-Valent Cobalt Complexes in Cat","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":null,"pages":null},"PeriodicalIF":5.2,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398355","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":"Engineering Neuroglobin for Synthesis of Chiral Organoborons via Carbene B–H Insertion","authors":"Li-Juan Sun,&nbsp;Huamin Wang,&nbsp;Jia-Kun Xu,&nbsp;Wenjing Niu,&nbsp;Shu-Qin Gao and Ying-Wu Lin*,&nbsp;","doi":"10.1021/acs.orglett.4c0331410.1021/acs.orglett.4c03314","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c03314https://doi.org/10.1021/acs.orglett.4c03314","url":null,"abstract":"<p >Organoborons have recently received much attention, while a biocatalytic platform for the synthesis of chiral organoborons is limited only to <i>Rma</i> cytochrome <i>c</i>. In this study, we exploited the other heme protein, neuroglobin (Ngb), and engineered a quadruple mutant, A15C/H64G/V68F/F28M Ngb, by redesigning the heme active site using the structural information on A15C Ngb and molecular docking studies. The enzyme was shown to be efficient in catalyzing carbene transfer B–H insertion reactions between pyridine/quinoline boranes and benzyl 2-diazopropanoates and their derivatives (29 examples). The designed cavity in the heme distal site favors the binding of large volume substrates such as those containing a quinoline, naphthyl, or biphenyl group. As further determined by the X-ray crystallography of <b>6c</b>, the chiral products are in the <i>R</i>-configuration, with up to 98:2 e.r. Furthermore, both the whole cell and cell lysate containing the enzyme are reactive toward the B–H insertion reactions. This study presents a convenient biocatalytic platform that may be generally applicable for the synthesis of functional chiral organoborons.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":null,"pages":null},"PeriodicalIF":4.9,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142450606","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":"Aliphatic Nitrile Template Enabled meta-C–H Olefination of Indene Enoate Esters under Microwave Accelerating Conditions","authors":"Kurella Mounika,&nbsp; and ,&nbsp;Gedu Satyanarayana*,&nbsp;","doi":"10.1021/acs.orglett.4c0335710.1021/acs.orglett.4c03357","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c03357https://doi.org/10.1021/acs.orglett.4c03357","url":null,"abstract":"<p >Site-selective activation of a particular remote C–H bond in molecules with multiple C–H bonds remains challenging in organic synthesis. In addition, evolving such transformations via the utilization of unconventional techniques is highly desirable. We demonstrated hitherto unexplored double bond geometry-guided and end-on nitrile-template-assisted <i>meta</i>-C–H functionalization of indene enoate esters under microwave-accelerated conditions. Significantly, the strategy exhibited broad compatibility concerning the substrates and olefin coupling partners. Remarkably, drug diversification has also been showcased.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":null,"pages":null},"PeriodicalIF":4.9,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142450669","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":"The Construction of Furocoumarins through Iron-Catalyzed Relay Annulation of Oxime Esters with 4-Hydroxycoumarins","authors":"Kun Jiang,&nbsp;Qing-Peng Liu,&nbsp;Yu-Qiang Zhou,&nbsp;Ning Yu,&nbsp;Lei Li and Ye Wei*,&nbsp;","doi":"10.1021/acs.orglett.4c0306310.1021/acs.orglett.4c03063","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c03063https://doi.org/10.1021/acs.orglett.4c03063","url":null,"abstract":"<p >An iron-catalyzed relay annulation protocol was disclosed, which utilizes oxime esters and 4-hydroxycoumarins as the readily available starting materials and showcases broad substrate scope and good functional group tolerance. This method allows the simultaneous generation of two C–C and one C–O bonds and two rings in one step, affording structurally new furocoumarins in moderate to good yields.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":null,"pages":null},"PeriodicalIF":4.9,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142450662","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":"The Construction of Furocoumarins through Iron-Catalyzed Relay Annulation of Oxime Esters with 4-Hydroxycoumarins","authors":"Kun Jiang, Qing-Peng Liu, Yu-Qiang Zhou, Ning Yu, Lei Li, Ye Wei","doi":"10.1021/acs.orglett.4c03063","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c03063","url":null,"abstract":"An iron-catalyzed relay annulation protocol was disclosed, which utilizes oxime esters and 4-hydroxycoumarins as the readily available starting materials and showcases broad substrate scope and good functional group tolerance. This method allows the simultaneous generation of two C–C and one C–O bonds and two rings in one step, affording structurally new furocoumarins in moderate to good yields.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":null,"pages":null},"PeriodicalIF":5.2,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398347","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":"Aliphatic Nitrile Template Enabled meta-C–H Olefination of Indene Enoate Esters under Microwave Accelerating Conditions","authors":"Kurella Mounika, Gedu Satyanarayana","doi":"10.1021/acs.orglett.4c03357","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c03357","url":null,"abstract":"Site-selective activation of a particular remote C–H bond in molecules with multiple C–H bonds remains challenging in organic synthesis. In addition, evolving such transformations via the utilization of unconventional techniques is highly desirable. We demonstrated hitherto unexplored double bond geometry-guided and end-on nitrile-template-assisted <i>meta</i>-C–H functionalization of indene enoate esters under microwave-accelerated conditions. Significantly, the strategy exhibited broad compatibility concerning the substrates and olefin coupling partners. Remarkably, drug diversification has also been showcased.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":null,"pages":null},"PeriodicalIF":5.2,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398485","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":"Synthesis, Structure, and Redox Properties of Nonsymmetric 6-Oxoverdazyls","authors":"Nagalexmi Mamveedu Saji,&nbsp;Madeleine R. Taylor,&nbsp;Daniel M. Mazzucato,&nbsp;Paul J. Low,&nbsp;Li Feng Lim,&nbsp;Nicholas Cox,&nbsp;Nicholas F. Chilton,&nbsp;Stephen A. Moggach,&nbsp;Gemma F. Turner,&nbsp;Marcus J. Giansiracusa,&nbsp;Colette Boskovic,&nbsp;Curtis C. Ho,&nbsp;Stuart C. Thickett,&nbsp;Melissa K. Stanfield,&nbsp;Alex C. Bissember and Rebecca O. Fuller*,&nbsp;","doi":"10.1021/acs.orglett.4c0285410.1021/acs.orglett.4c02854","DOIUrl":"https://doi.org/10.1021/acs.orglett.4c02854https://doi.org/10.1021/acs.orglett.4c02854","url":null,"abstract":"<p >Nonsymmetric 6π-electron (“oxidized”) 6-oxoverdazyls have been synthesized for the first time. After formal incorporation of a hydrogen atom, the corresponding 7π-electron neutral verdazyl radical is generated. The 7π radical can undergo a further electrochemically reversible reduction to an 8π anion. Both redox processes occur at more moderate potentials than the parent verdazyl, tuning the accessible potential windows of 6π, 7π, and 8π verdazyl species.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":null,"pages":null},"PeriodicalIF":4.9,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142450668","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}