Organic chemistry frontiers : an international journal of organic chemistry最新文献

A regioselective and sustainable approach for the synthesis of substituted thieno[2,3-b]chromen-4-ones with pendant imine groups via a base-promoted multicomponent reaction† 碱基促进多组分反应合成含亚胺基取代噻吩[2,3-b]铬-4- 1的区域选择性和可持续性研究

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-03-03 DOI: 10.1039/d5qo00228a

Ujjwal Jyoti Goswami , Anjela Xalxo , Abu Taleb Khan

引用次数: 0

Synthesis of challenging cyclic tetrapeptides using machine learning-assisted high-throughput continuous flow technology† 利用机器学习辅助高通量连续流技术合成具有挑战性的环四肽

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-03-03 DOI: 10.1039/d4qo02225d

Chaoyi Li , Jiaping Yu , Wanchen Li , Jingyuan Liao , Junrong Huang , Jiaying Liu , Wei Zhao , Yinghe Zhang , Yuxiang Zhu , Hengzhi You

{"title":"Synthesis of challenging cyclic tetrapeptides using machine learning-assisted high-throughput continuous flow technology†","authors":"Chaoyi Li , Jiaping Yu , Wanchen Li , Jingyuan Liao , Junrong Huang , Jiaying Liu , Wei Zhao , Yinghe Zhang , Yuxiang Zhu , Hengzhi You","doi":"10.1039/d4qo02225d","DOIUrl":"10.1039/d4qo02225d","url":null,"abstract":"<div><div>Cyclic tetrapeptides (CTPs), which possess unique structures and diverse biological activities, are significant compounds in pharmaceutical and therapeutic applications. However, the inherent ring strain in CTPs poses challenges in minimizing racemization and achieving high yields. The antiviral CTP <em>cyclo</em>-(Pro-Leu)<sub>2</sub> and the anticancer CTP <em>cyclo</em>-(Pro-Val)<sub>2</sub> were previously reported with yields of only 5% and 7%, respectively. The wide range of peptide cyclization conditions significantly influences the reaction outcomes, making comprehensive optimization a labor-intensive process. Herein, we integrated high-throughput continuous flow technology with machine learning to achieve rapid and comprehensive optimization for the synthesis of challenging CTPs, achieving a 5- to 7-fold increase in yields for both <em>cyclo</em>-(Pro-Val)<sub>2</sub> and <em>cyclo</em>-(Pro-Leu)<sub>2</sub> compared to those reported in the literature. Notably, with the aid of machine learning, which achieves a root mean square error of 3.6, the optimization workload can be reduced by up to 90%. These advancements may offer a solution for the rapid optimization and synthesis of valuable CTPs.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 10","pages":"Pages 3208-3214"},"PeriodicalIF":0.0,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143546820","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Pd-catalyzed site-specific heteroaromatic C–H/peri-C–H annulative coupling for synthesis of cyclopenta-fused polycyclic heteroarenes† pd催化位点特异性杂芳烃C-H/环- h环结偶联合成环五聚杂环芳烃

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-03-03 DOI: 10.1039/d5qo00034c

Tienan Jin , Masaki Kawata , Sho Aida , Masahiro Terada

{"title":"Pd-catalyzed site-specific heteroaromatic C–H/peri-C–H annulative coupling for synthesis of cyclopenta-fused polycyclic heteroarenes†","authors":"Tienan Jin , Masaki Kawata , Sho Aida , Masahiro Terada","doi":"10.1039/d5qo00034c","DOIUrl":"10.1039/d5qo00034c","url":null,"abstract":"<div><div>Cyclopenta-fused polycyclic heteroarenes (CP-PHAs) composed of acenaphthylene and heteroaromatic units have emerged as intriguing photoelectronic materials in view of the electron-accepting feature of the fused CP rings and the tunable electronic properties of the heteroaromatics. To date, Pd-catalyzed aromatic C–H/<em>peri</em>-C–halogen coupling has been used as one of the most general methods to construct such CP-rings. In contrast, Pd-catalyzed direct aromatic C–H/<em>peri</em>-C–H coupling may provide a shortcut to this CP-ring formation, which is applicable to a wide range of polycyclic arenes bearing <em>peri</em>-C–H bonds, but remains unexploited so far. We herein describe a Pd-catalyzed site-specific C–H/<em>peri</em>-C–H annulative coupling between (benzo)thiophenes or indoles with various polycyclic arenes to access a variety of π-extended CP-PHAs. Benzo[<em>b</em>]thiophenes or thiophenes with a 1-naphthalenyl group at the C3 position gave C2-naphthylated CP-PHAs in the Pd(OPiv)<sub>2</sub>/AgOPiv system, whereas indoles with a 1-naphthalenyl group at the C2 position gave C3-naphthylated CP-PHAs in the Pd(OPiv)<sub>2</sub>/AgSbF<sub>6</sub> system. Notably, deuteration experiments demonstrated that silver salts play a crucial role in the formation of heteroaryl-Ag species <em>via</em> site-specific C–H metalation of heteroaromatics, which subsequently undergo transmetalation with Pd(<span>ii</span>) to form heteroaryl-Pd species and activate the <em>peri</em>-C–H bond of the naphthalene group. Furthermore, this method enables the synthesis of structurally diverse CP-PHAs <em>via</em> activation of <em>peri</em>-C–H bonds in large polycyclic aromatic hydrocarbons such as anthracene, phenanthrene, and pyrene.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 10","pages":"Pages 3230-3238"},"PeriodicalIF":0.0,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143546818","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Radical-mediated sulfonylation relay of alkyl alkynes/alkenes and electron-deficient alkenes to access vinyl and alkyl sulfones† 烷基炔/烯烃和缺电子烯烃的自由基介导的磺化反应以获得乙烯基和烷基砜

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-03-03 DOI: 10.1039/d5qo00214a

Jin-Hui Liu , Fang Long , Qing Li , Da-Zhi Sun , Ying Man , Lin Wang , Li-Jun Wu , Shuang-Feng Yin

{"title":"Radical-mediated sulfonylation relay of alkyl alkynes/alkenes and electron-deficient alkenes to access vinyl and alkyl sulfones†","authors":"Jin-Hui Liu , Fang Long , Qing Li , Da-Zhi Sun , Ying Man , Lin Wang , Li-Jun Wu , Shuang-Feng Yin","doi":"10.1039/d5qo00214a","DOIUrl":"10.1039/d5qo00214a","url":null,"abstract":"<div><div>Achieving sulfonylation relay reactions between two distinct alkynes/alkenes remains a significant challenge due to inherent reactivity and selectivity issues. Herein, we report a radical-mediated sulfonylation relay of alkyl alkynes/alkenes and electron-deficient alkenes using Na<sub>2</sub>S<sub>2</sub>O<sub>4</sub> as a linker for the synthesis of highly selective (<em>Z</em>)-vinyl and alkyl sulfones. Notably, Na<sub>2</sub>S<sub>2</sub>O<sub>4</sub> serves not only as a convenient SO<sub>2</sub> source but also as an electron donor, obviating the need for metal catalysts and additional reductants typically required in conventional approaches. The protocol exhibits an excellent substrate scope and functional group tolerance, accommodating bioactive scaffolds with high efficiency. Mechanistic investigations revealed that the transformation proceeds <em>via</em> a radical pathway, with deuterium-labeling experiments confirming that the hydrogen atom in the protonation step predominantly originates from water.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 10","pages":"Pages 3299-3305"},"PeriodicalIF":0.0,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635460","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Photo-induced copper-catalyzed controllable denitrogenation/SO2 insertion of aryltriazenes: divergent synthesis of aryl sulfonamides and diaryl sulfones† 光诱导铜催化芳基三嗪的可控脱氮/SO2插入：芳基磺酰胺和二芳基砜的发散合成

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-03-03 DOI: 10.1039/d4qo02382j

Bin Wang , Chenglong Wang , Tingting Zhang , Ziren Chen , Yu Xia , Shaofeng Wu , Yonghong Zhang , Chenjiang Liu

引用次数: 0

Cu(ii)-catalyzed asymmetric Mukaiyama–Michael reaction: concise synthesis of cyclohexadiene analogues† Cu（II）催化不对称Mukaiyama - Michael反应：环己二烯类似物的简明合成

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-03-03 DOI: 10.1039/d5qo00237k

Ning Li , Jun-Hao Zhang , Wei-Jing Yang , Ming-Sheng Xie , Hai-Ming Guo

引用次数: 0

Protodefluorinated Selectfluor® heteroaggregate photoinduces direct C(sp3)–H fluorinations without photocatalyst† 一种原去氟化selectflu®异质聚集体光诱导直接C(sp3)−H氟化无光催化剂

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-03-03 DOI: 10.1039/d5qo00149h

Shahboz Yakubov , Joshua P. Barham

{"title":"Protodefluorinated Selectfluor® heteroaggregate photoinduces direct C(sp3)–H fluorinations without photocatalyst†","authors":"Shahboz Yakubov , Joshua P. Barham","doi":"10.1039/d5qo00149h","DOIUrl":"10.1039/d5qo00149h","url":null,"abstract":"<div><div>Herein, we uncover a hitherto hidden role of – a cheap, stable, recoverable by-product of radical C(sp<sup>3</sup>)–H fluorinations using Selectfluor®. This forms a photoactive, mixed heteroaggregate with Selectfluor® which underlies the reactivity of visible light photochemical fluorination reactions of unactivated C(sp<sup>3</sup>)–H bonds. Where previous reports claim to be ‘photocatalytic’, reactions work without photocatalyst when is dosed in at the start. Our results demonstrate that ‘photocatalysts’ are only necessary to generate a sufficient amount of nascent , whose heteroaggregate with Selectfluor® takes over as the main photoactive species. Mechanistic studies suggest the formation of a heteroaggregate between and Selectfluor® under photoirradiation, which generates . A salient feature of our <strong>H-TEDA(BF</strong><sub><strong>4</strong></sub><strong>)</strong><sub><strong>2</strong></sub>-promoted method is its flexibility to use the C(sp<sup>3</sup>)–H precursor substrate as the limiting reactant, simplifying product isolations.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 10","pages":"Pages 3156-3162"},"PeriodicalIF":0.0,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143443951","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Dearomatization/rearomatization model for copper-mediated quinoline N-oxide C–H functionalization† 铜介导的喹啉n -氧化物C-H功能化的脱芳/重芳模型

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-03-03 DOI: 10.1039/d5qo00028a

Wenxuan Lin , Wei Lai , Lei Xu , Xin Dai , Lin Zhang , Xiaoqian He , Li-Li Liao , Yu Lan , Ruopeng Bai

{"title":"Dearomatization/rearomatization model for copper-mediated quinoline N-oxide C–H functionalization†","authors":"Wenxuan Lin , Wei Lai , Lei Xu , Xin Dai , Lin Zhang , Xiaoqian He , Li-Li Liao , Yu Lan , Ruopeng Bai","doi":"10.1039/d5qo00028a","DOIUrl":"10.1039/d5qo00028a","url":null,"abstract":"<div><div>Transition metal-catalyzed direct heteroarene C–H functionalization is a powerful strategy to access heteroarene derivatives with improved atom and step economy. In addition to commonly proposed concerted metalation deprotonation (CMD) and electrophilic aromatic substitution (S<sub>E</sub>Ar) models, we herein establish a copper-catalyzed dearomatization/rearomatization strategy for the C–H functionalization of electron-deficient heteroarenes, exemplified by quinoline <em>N</em>-oxides. Computational studies suggest a distinct pathway involving a 1,3-dipolar addition between quinone <em>N</em>-oxide and benzyl Cu(<span>i</span>). Subsequent deprotonation or base-assisted δ-elimination gives a borylative alkylation or alkenylation product. Nucleus-independent chemical shift (NICS) analysis confirms that dearomatization occurs in the 1,3-dipolar addition step and the deprotonation/δ-elimination process involves rearomatization. This dearomatization/rearomatization pathway provides an alternative approach to achieve C2–H functionalization of electron-deficient heteroarenes under mild conditions.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 10","pages":"Pages 3246-3255"},"PeriodicalIF":0.0,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143575129","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Photoelectrochemical upcycling of PVC plastic waste for the synthesis of chlorinated quinolinone derivatives† 聚氯乙烯塑料废弃物的光电升级利用合成氯化喹啉酮衍生物

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-03-03 DOI: 10.1039/d5qo00189g

Kai Zheng , Jingwen He , Lixi Zhang , Zhaoyang Wang , Pengfei Zhang , Jianyu Cao , Chao Shen

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Synthesis of oxylipids via a boronic ester cycloetherification approach† 硼酯环醚化法合成氧脂类

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-03-03 DOI: 10.1039/d5qo00213c

Markus Tost , Uli Kazmaier

引用次数: 0