{"title":"Photoinduced Cu-Catalyzed C2-H Functionalization of Azoles using Aryl Thianthrenium Salts","authors":"Zhenhui Wang, Jinfang Wang, Zhenning Yang, Xinyao Li, Kaining Cheng, wei liu","doi":"10.1002/adsc.202401378","DOIUrl":"https://doi.org/10.1002/adsc.202401378","url":null,"abstract":"Development of a mild approach for the highly efficient synthesis of 2-aryl azoles, which are typically synthesized using high temperature, ligands and preactivated substrates, is highly desirable. Here, we report a mild and efficient photo-induced Cu-catalyzed C–H/C–H cross-coupling to obtain C2-functionalized azoles using aryl thianthrenium salt (Ar-TTs). The reaction exhibits a broad substrate scope and an excellent functional group compatibility and serves as an ideal strategy for the late-stage functionalization of pharmaceuticals. Additionally, this method enables the efficient synthesis of azole-based polycyclic compounds.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"239 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142810024","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}
Xiaochong Guo, Bin Xiao, Kangping Wu, Mianling Zhang, Haixiang Hu
{"title":"Recent Advances in Photoredox/Chromium dual‐Catalyzed Carbonyl Addition Reactions: A Review","authors":"Xiaochong Guo, Bin Xiao, Kangping Wu, Mianling Zhang, Haixiang Hu","doi":"10.1002/adsc.202401315","DOIUrl":"https://doi.org/10.1002/adsc.202401315","url":null,"abstract":"The chromium‐catalysed Nozaki‐Hiyama‐Kishi (NHK) reaction is a very dependable technique for alcohol synthesis and is extensively used in the complete synthesis of natural compounds. The majority of these reactions occur via a reductive‐radical‐polar crossover (RRPCO) mechanism, which is crucial for the transformation of reactive radical intermediates. The production of radicals using photoinduced catalytic reactions is now among the most effective approaches. The photoinduced chromium‐catalysed addition reaction to carbonyl compounds is an effective technique for alcohol synthesis that integrates the benefits of photocatalysis with chromium catalysis. Photocatalysis significantly enhances the diversity of radical production, hence broadening the substrate scope in the chromium‐catalysed NHK reaction. This paper primarily examines the photoredox chromium dual‐catalysed carbonyl addition process for alcohol synthesis, including numerous methods for radical generation.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"15 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142804923","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}
Chenxing Zhou, Xin Zhang, Peiqin Zhang, Congde Huo
{"title":"Decyanative arylation via radical coupling","authors":"Chenxing Zhou, Xin Zhang, Peiqin Zhang, Congde Huo","doi":"10.1002/adsc.202401285","DOIUrl":"https://doi.org/10.1002/adsc.202401285","url":null,"abstract":"Arenes, especially heteroarenes, are crucial structural motifs in organic chemistry, pharmaceutical chemistry, and materials science. The introduction of (hetero)aryl groups using readily available feedstocks to modify organic chemicals is a significant topic. Nitriles are ubiquitous and versatile building blocks in organic synthesis. This article summarizes recent advances in decyanative arylation via radical cross-coupling reactions. In these transformations, (hetero)aromatic nitriles undergo one-electron reduction to form persistent radical anion intermediates. Simultaneously, transient carbon centered radicals are generated through cleavage of C–H, C–C, C–X (where X = B, N, Si, S, Br) bonds through single electron transfer or hydrogen atom transfer processes. Finally, a radical-radical coupling reaction followed by CN elimination leads to the formation of aromatized products.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"21 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142810023","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}
Dilip V. Patil, Rahul Patel, Shinobu Takizawa, Hun Young Kim, Kyungsoo Oh
{"title":"Tandem Photocatalyst-Free Visible Light Aryl Azidation−Intramolecular C−H Amination: One-Pot Access to Carbazoles and Indoles from Areneazo-2-(2-nitro)propanes","authors":"Dilip V. Patil, Rahul Patel, Shinobu Takizawa, Hun Young Kim, Kyungsoo Oh","doi":"10.1002/adsc.202401333","DOIUrl":"https://doi.org/10.1002/adsc.202401333","url":null,"abstract":"The visible light-induced one-pot tandem photolysis of areneazo-2-(2-nitro)propanes was achieved to give carbazole and indole derivatives. The aryl azidation followed by an intramolecular C−H amination smoothly proceeded under visible light irradiation without any photocatalyst, demonstrating the synthetic versatility of areneazo-2-(2-nitro)propanes. The in situ generation of aryl azide intermediates was executed under mild visible light photolysis conditions, showcasing the synthetic versatility of areneazo-2-(2-nitro)propanes, a safe alternative of diazonium salts.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"2 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142810022","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}
Lena Brassart, Maxime Manneveau, Thomas Poisson, Julien LEGROS, Philippe Huez, Massimiliano Forcato, PHILIPPE JUBAULT, Laetitia Chausset-Boissarie
{"title":"Continuous Flow Synthesis of α‐Chloroketones from Esters","authors":"Lena Brassart, Maxime Manneveau, Thomas Poisson, Julien LEGROS, Philippe Huez, Massimiliano Forcato, PHILIPPE JUBAULT, Laetitia Chausset-Boissarie","doi":"10.1002/adsc.202401438","DOIUrl":"https://doi.org/10.1002/adsc.202401438","url":null,"abstract":"Herein, we report a novel and practical strategy to access α‐chloroketones from esters bearing diverse (hetero)aromatic, aliphatic, alkynyl and alkenyl substituents with transient chloromethyllithium under continuous flow conditions. This highly chemoselective method enables a fast (on a time scale of <5 s), efficient and straightforward access to a broad substrate scope (up to 99% yield) with a remarkable throughput of ∼10.6 g/h.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"77 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142804822","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}
Tian-Yu Ding, Xiao-Ning Guo, Bin Chen, Chen-Ho Tung, Li-Zhu Wu
{"title":"Photocatalytic C-I Bond Borylation and Phosphorylation of Diaryliodonium Salts with Excellent Atom-Economy","authors":"Tian-Yu Ding, Xiao-Ning Guo, Bin Chen, Chen-Ho Tung, Li-Zhu Wu","doi":"10.1002/adsc.202401240","DOIUrl":"https://doi.org/10.1002/adsc.202401240","url":null,"abstract":"Highly atom-economic conversion of diaryliodonium salts represents an underdeveloped but highly desirable domain. Most reactions involving these species only utilize single aryl group of the diaryliodonium and produce an equivalent of aryl iodide as waste. Herein, by further transforming the side-product aryl iodide, we report an overall new two-step one-pot strategy that allows photocatalytic C−I bond borylation and phosphorylation of diaryliodonium salts and ensures effective conversion of both aryl groups of the diaryliodonium into the relevant arylboronic esters or arylphosphonic esters. Mechanistic investigations suggest that electron-donor-acceptor (EDA) complex is formed between the photocatalyst phenothiazine (PTH) and diaryliodonium salt substrate. Upon visible light irradiation, this complex produces aryl radical and aryl iodide. With addition of a base in the second step, the reducing ability of the photocatalyst is enhanced via proton-coupled electron transfer (PCET) process, thereby aryl iodide produced in the first step is reduced to yield aryl radical again. Both aryl radicals generated in the two steps react with B2(OR)4 or P(OR)3 to produce the corresponding monoarylation product in a quantitative yield.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"20 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142797653","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}
Celeste Nobbio, William R. Birmingham, Elisabetta Brenna, Nicholas J. Turner, Davide Tessaro, Fabio Parmeggiani
{"title":"Stereoselective Synthesis of Aliphatic α-Amino Acids by Chemo-Enzymatic Hydroamination-Hydrodesulfurisation","authors":"Celeste Nobbio, William R. Birmingham, Elisabetta Brenna, Nicholas J. Turner, Davide Tessaro, Fabio Parmeggiani","doi":"10.1002/adsc.202401223","DOIUrl":"https://doi.org/10.1002/adsc.202401223","url":null,"abstract":"Phenylalanine ammonia lyase (PAL) enzymes have been extensively exploited to produce differently substituted arylalanine analogues, but their use in the stereoselective synthesis of aliphatic fatty amino acids has never been addressed. In this work, a two-step hydroamination-hydrodesulfurisation process has been investigated for the production of aliphatic L-α-amino acids from thienylacrylic acids, easily accessible by condensation from the corresponding arylaldehyde. Wild-type PALs from Planctomyces brasiliensis and Streptomyces rimosus were selected as the most promising candidates and improved by site-directed mutagenesis, thus unlocking the hydroamination of a broad panel of 10 different thienylacrylic acids bearing aliphatic and aromatic substituents. The subsequent hydrodesulfurisation step, accomplished by means of inexpensive Raney nickel in mild conditions and aqueous medium, afforded the corresponding aliphatic α-amino acids in 10-63% overall isolated yield and perfect enantiopurity. This chemo-enzymatic process represents the first example of aliphatic amino acid production using PALs, circumventing a major limitation of those biocatalysts.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"28 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793799","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":"Chemo- and Enantioselective Intermolecular Allylation of Quinolin-2-ones","authors":"Zihao Li, Yumeng Wang, Yuqiao Zhou, Zongli Xiong, Jian Wang, Weijun Yao, Zhen Wang","doi":"10.1002/adsc.202401113","DOIUrl":"https://doi.org/10.1002/adsc.202401113","url":null,"abstract":"An enantioselective C-, O- and N- intermolecular allylic reaction of quinolin-2(1H)-ones has been developed. The reaction between 3-hydroxy quinolone and Boc-protected MBH adducts with Pd-catalysis provided a series of 1,4-dihydroquinoline-2,3-diones in 20-95% yield accompanied by 69-96% enantioselectivity. In addition, the O-allylic alkylation could occur by varying the organo-catalyst and Boc-protected MBH adducts from benzaldehyde. Furthermore, the N-allylation of 3-O-protected quinolin-2-ones with allylic acetates was also realized (40-92% yield, 78-97% ee).","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"115 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793798","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}
Bin Dong, Zhiming Li, Wei Li, Jiang Deng, Junyuan Yan, Yihan Guo, Kai-Kai Wang, Shan Qian, Zhouyu Wang, Xiao-Long He
{"title":"Temperature-Controlled Dearomative [5+1] Spiroannulation and Formal [5+2] Cyclization of Indoles with Enynones: Divergent Synthesis of Spiro-Indolenines and Dihydrocyclohepta[b]Indolones","authors":"Bin Dong, Zhiming Li, Wei Li, Jiang Deng, Junyuan Yan, Yihan Guo, Kai-Kai Wang, Shan Qian, Zhouyu Wang, Xiao-Long He","doi":"10.1002/adsc.202401072","DOIUrl":"https://doi.org/10.1002/adsc.202401072","url":null,"abstract":"<p>We developed a temperature-controlled intermolecular dearomative [5+1] spiroannulation and [5+2] cyclization of indoles with enynones, smoothly delivering a variety of spiroindolenines and dihydrocyclohepta[<i>b</i>]indolones under 40 °C and 80 °C, respectively. A three-step cascade reaction was also realized by using OTBS or NHBoc containing enynones in the reaction with the indole under the identical condition. And a novel valuable highly-oriented three-dimensional indole-based tetracyclic scaffold was produced in high yields with excellent diastereoselectivities. Additionally, various spiroindolines and spirooxindoles were facilely produced through simple operations. This highly efficient domino-reaction represents an emblematic method for the preparation of indole-based polycycles through the intermolecular pathway.</p>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"9 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793797","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":"Metal‐free visible‐light‐induced direct synthesis of alkyl‐substituted phosphonodithioates from white phosphorus (P4)","authors":"Fengxiao Wang, Xiyuan Zhang, Jiaming Xu, Qitao Shen, Bo Jiang, Zhiwei Miao","doi":"10.1002/adsc.202401355","DOIUrl":"https://doi.org/10.1002/adsc.202401355","url":null,"abstract":"The direct synthesis of organic phosphorus compounds from white phosphorus (P4) is a longstanding challenge in organic synthesis. Here, we present a novel visible light‐induced three‐component functionalization reaction that integrates P4, disulfide compounds, and N‐hydroxyphthalimide (NHPI) esters to produce alkyl‐substituted phosphonodithioates in a one‐pot process. Using 2,4,5,6‐tetrakis(carbazol‐9‐yl)‐1,3‐dicyanobenzene (4CzIPN) as a photocatalyst, blue LEDs (456 nm) as the light source, and N,N‐diisopropylethylamine (DIPEA) as the reducing agent in an acetone‐toluene solvent system, this method achieves moderate to good yields of structurally diverse phosphonodithioates. The reaction proceeds under mild conditions, ensures complete conversion of P4, avoids chlorination, and uses inexpensive, readily available starting materials, offering potential for large‐scale applications.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"221 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142788446","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}