{"title":"Halophosphonium Salts-Mediated Photochemical C(sp3)–H Functionalization","authors":"Kaiting Sun, , , Xun Yang, , , Youyou Zheng, , , Wenlu Sun, , , Boyang He, , , Shuyu Huang, , and , Shihui Liu*, ","doi":"10.1021/acs.orglett.5c03758","DOIUrl":"10.1021/acs.orglett.5c03758","url":null,"abstract":"<p >Herein we report a method that uses halophosphonium salts as dual-function reagents for versatile C(sp<sup>3</sup>)–H functionalization under visible light. They serve simultaneously as photocatalysts and hydrogen atom transfer reagents, eliminating the need for exogenous metal catalysts. This strategy enables benzylic, allylic, and aliphatic C–H alkylation, hydrazination, and cyanation. The discovery significantly expands the synthetic utility of halophosphonium salts beyond their classical roles, establishing them as modular photochemical scaffolds for green organic synthesis.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"27 39","pages":"11143–11148"},"PeriodicalIF":5.0,"publicationDate":"2025-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145089700","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 : 2025-09-19DOI: 10.1021/acs.orglett.5c03411
Dinesh G. Thakur, Mahesh A. Sonawane, Raj N. Patel, Subhash Chandra Ghosh
{"title":"Palladium-Catalyzed Synthesis of Quinolinyl Lactones via Double C(sp3)–H Functionalization","authors":"Dinesh G. Thakur, Mahesh A. Sonawane, Raj N. Patel, Subhash Chandra Ghosh","doi":"10.1021/acs.orglett.5c03411","DOIUrl":"https://doi.org/10.1021/acs.orglett.5c03411","url":null,"abstract":"We have developed a novel palladium-catalyzed method for synthesizing quinolinyl lactones via double C(sp<sup>3</sup>)–H functionalization. This atom-economical strategy utilizes a bifunctional 2-iodobenzoic acid reagent in a single catalytic cycle. An optimized solvent mixture of hexafluoro-2-propanol and acetic acid significantly enhanced reactivity and selectivity. This work provides a valuable, site-selective pathway for creating complex quinolinyl lactone scaffolds.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"74 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145089703","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":"Intermolecular Double C–H Annulation via 1,4-Pd Migration: A Modular Strategy for Heteropolycycle Construction","authors":"Zhendong Cheng, , , Siqi Li, , , Yanling Zhang, , , Zhiwei Li, , , Yun Liang*, , and , Yuan Yang*, ","doi":"10.1021/acs.orglett.5c03264","DOIUrl":"10.1021/acs.orglett.5c03264","url":null,"abstract":"<p >Herein, we report a 1,4-Pd migration-enabled intermolecular double C–H annulation between alkene-tethered aryl halides (e.g., 2-iodo-<i>N</i>-methacryloylbenzamides and 2-(2-iodophenyl)-1<i>H</i>-indoles) and 1,<i>n</i>-diynes. This transformation proceeds through a cascade sequence involving Heck cyclization, alkyl-to-aryl 1,4-Pd migration, double alkyne insertion, and C–H activation, enabling the remote construction of structurally diverse heteropolycycles, including tetracyclic fused isoquinolinediones and hexacyclic indolo[2,1-<i>a</i>]isoquinolinones. The method exhibits a broad substrate scope and excellent regioselectivity.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"27 39","pages":"10999–11004"},"PeriodicalIF":5.0,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145083412","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 : 2025-09-19DOI: 10.1021/acs.orglett.5c03140
Jan Dudziński, , , Damian Antoniak, , , Kacper Błaziak, , and , Michał Barbasiewicz*,
{"title":"Beyond Friedel–Crafts: Spontaneous and Fluoride-Catalyzed Acylation of 2-(Trialkylsilyl)pyridines","authors":"Jan Dudziński, , , Damian Antoniak, , , Kacper Błaziak, , and , Michał Barbasiewicz*, ","doi":"10.1021/acs.orglett.5c03140","DOIUrl":"10.1021/acs.orglett.5c03140","url":null,"abstract":"<p >2-(Trialkylsilyl)pyridines react spontaneously with acyl chlorides to give 2-pyridyl ketones in high yields. The process consists of four elementary steps of <i>N</i>-acylation, desilylation, <i>C</i>-acylation, and <i>N</i>-deacylation and results in a selective monosubstitution at the carbonyl group. The key step in this mechanism is the intrinsic generation of a stabilized ylide (Hammick intermediate), which acts as a nucleophile. For the functionalization of complex molecules, an alternative fluoride-catalyzed protocol utilizing more stable acyl fluorides has been developed.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"27 39","pages":"10954–10961"},"PeriodicalIF":5.0,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.orglett.5c03140","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145089701","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":"Pd/C-Catalyzed Hydrocarboxylation and Carbonylative Esterification of Indoles to Indole-3-carboxylic Acids and Esters","authors":"Poonam Sharma, , , Pushkar Mehara, , , Ashish Kumar, , and , Pralay Das*, ","doi":"10.1021/acs.orglett.5c03216","DOIUrl":"10.1021/acs.orglett.5c03216","url":null,"abstract":"<p >An unprecedented and robust Pd/C catalytic platform has been introduced for regioselective hydrocarboxylation as well as carbonylative esterification of indoles with aliphatic alcohols employing oxalic acid as the CO precursor. The developed strategy efficiently enables the synthesis of diverse classes of indole-3-carboxylic acids and esters with excellent regioselectivity and good yields under mild reaction conditions. Notably, phosphine ligand-free conditions, utilization of economical and bench-stable oxalic acid as the C1 source, commercially accessible and reusable Pd/C as a catalyst, and gram scale applicability are the additional benefits of the established methodology.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"27 39","pages":"10974–10979"},"PeriodicalIF":5.0,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145089702","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 : 2025-09-19DOI: 10.1021/acs.orglett.5c03404
Ilya D. Deltsov, , , Dmitry B. Vinogradov, , , Konstantin A. Monogarov, , and , Leonid L. Fershtat*,
{"title":"Oxadiazole Alliance with an Aminodinitrophenyl Scaffold: En Route to Heat-Resistant Friction-Insensitive Energetic Materials","authors":"Ilya D. Deltsov, , , Dmitry B. Vinogradov, , , Konstantin A. Monogarov, , and , Leonid L. Fershtat*, ","doi":"10.1021/acs.orglett.5c03404","DOIUrl":"10.1021/acs.orglett.5c03404","url":null,"abstract":"<p >A set of new energetic materials composed of 1,2,5-oxadiazole moieties coupled with the 4-amino-3,5-dinitrophenyl scaffold through the 1,2,4-oxadiazole linker was designed and synthesized. Synthesized energetic substances exhibit high densities (1.66–1.74 g cm<sup>–3</sup>), positive enthalpies of formation (17–572 kJ mol<sup>–1</sup>), and high combined nitrogen–oxygen content (61–67%). Advantageously, newly prepared materials showed high thermal stability (up to 251 °C) and complete insensitivity to friction while retaining good detonation velocities (6.9–7.2 km s<sup>–1</sup>). Overall, fine modulation of oxadiazole and nitroaromatic scaffolds represents a good strategy for an assembly of balanced and heat-resistant energetic materials.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"27 39","pages":"11033–11037"},"PeriodicalIF":5.0,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145083410","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 : 2025-09-19DOI: 10.1021/acs.orglett.5c03111
Pengfei Li, , , Fan Wu, , , Chulin Qu, , , Hidemitsu Uno*, , and , Zhen Shen*,
{"title":"Two Cationic Antiaromatic Free-Base Corroles","authors":"Pengfei Li, , , Fan Wu, , , Chulin Qu, , , Hidemitsu Uno*, , and , Zhen Shen*, ","doi":"10.1021/acs.orglett.5c03111","DOIUrl":"10.1021/acs.orglett.5c03111","url":null,"abstract":"<p >The synthesis of free-base antiaromatic porphyrinoids remains a challenging task. Herein we report the first preparation of two cationic free-base antiaromatic corroles, <b>BC(H</b><sub><b>2</b></sub><b>)</b><sup><b>+</b></sup> (containing two NH moieties, slightly saddle-shaped) and <b>BC(H</b><sub><b>4</b></sub><b>)</b><sup><b>3+</b></sup> (containing four NH moieties, severely distorted saddle-shaped), utilizing a strategy of β-annulated benzene rings to suppress side reactions. The antiaromatic character of <b>BC(H</b><sub><b>2</b></sub><b>)</b><sup><b>+</b></sup> and <b>BC(H</b><sub><b>4</b></sub><b>)</b><sup><b>3+</b></sup> is robustly supported by crystallographic analysis, spectroscopic evidence, and theoretical calculations.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"27 39","pages":"10948–10953"},"PeriodicalIF":5.0,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145084098","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":"Visible-Light-Induced Palladium-Mediated Allylic C–H Alkylation Reaction","authors":"Kun-Yu Huang, , , Wei-Dong Lu, , , Xiao-Qing Chen, , , Kai Chen, , , Yu Zheng*, , and , Hua Yang*, ","doi":"10.1021/acs.orglett.5c03515","DOIUrl":"10.1021/acs.orglett.5c03515","url":null,"abstract":"<p >Direct C–H alkylation is one of the most important C–C bond formation events and is crucial to the efficient assembly of functionalized carbon skeletons in synthetic chemistry. We report herein a photoinduced palladium-catalyzed strategy for the direct alkylation of allylic C–H bonds. The success of this transformation relies on the use of 2-bromo-1,3-dimethylbenzene as a hydrogen atom transfer (HAT) mediator, in combination with a carbon nucleophile, facilitated by a palladium catalyst activated by blue light. Unlike classical Pd(II/0) pathways, this approach leverages the versatile reactivity of Pd(0/I/II) species through visible-light excitation, establishing a robust foundation for the feasibility of this synthetic methodology.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"27 39","pages":"11083–11088"},"PeriodicalIF":5.0,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145089544","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 : 2025-09-19DOI: 10.1021/acs.orglett.5c03582
Samrat Mallick, , , Pooja Bhardwaj, , , Dipankar Das, , and , Suman De Sarkar*,
{"title":"Electrochemical Formal (3 + 2) Cycloaddition/Imidation Cascade: Easy Access to Triazabicyclo-[3.3.0] Scaffolds","authors":"Samrat Mallick, , , Pooja Bhardwaj, , , Dipankar Das, , and , Suman De Sarkar*, ","doi":"10.1021/acs.orglett.5c03582","DOIUrl":"10.1021/acs.orglett.5c03582","url":null,"abstract":"<p >The established strategy unveils an electrochemical formal (3 + 2) cycloaddition/imidation sequence between <i>N</i>-aryl glycinamides and 5-methoxyoxazoles, furnishing diversely substituted imidazoline fused pyrrole-2,5-dione scaffolds. This diastereocontrolled cascade annulation operates with the assistance of ZnCl<sub>2</sub> as a Lewis acid catalyst and provides two contiguous stereocenters as part of the [3.3.0]triazabicyclic core structure. An extensive range of distinct functionalities is well tolerated under this mild electrochemical condition, contributing to a broad substrate scope.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"27 39","pages":"11117–11124"},"PeriodicalIF":5.0,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145089704","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 : 2025-09-18DOI: 10.1021/acs.orglett.5c03550
Fucong Dong, , , Jiye Shu, , , Jin Yang, , , Shaolei Xia, , and , Xiaodong Xiong*,
{"title":"Modular Access to Sulfondiimidoyl Fluorides by NaH-Mediated Fluorination of Sulfenamides","authors":"Fucong Dong, , , Jiye Shu, , , Jin Yang, , , Shaolei Xia, , and , Xiaodong Xiong*, ","doi":"10.1021/acs.orglett.5c03550","DOIUrl":"10.1021/acs.orglett.5c03550","url":null,"abstract":"<p >Despite the significant applications of sulfondiimidoyl fluorides in medicinal chemistry, efficient methods for preparing these valuable fluorinated structures remain limited. Herein, we disclose a straightforward method for the modular synthesis of symmetric and unsymmetric sulfondiimidoyl fluorides through sequential amination and oxidation of sulfinimidoyl fluoride at room temperature. The resulting sulfondiimidoyl fluorides could be converted into a diverse array of sulfondiimines, sulfondiimidate esters, and sulfondiimidamides by SuFEx reaction. Moreover, a first proof of concept for an asymmetric protocol by employing a quinidine derivative catalyst is reported.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"27 38","pages":"10908–10915"},"PeriodicalIF":5.0,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145077893","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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