Tianlei Du , Qiujie Qin , Jin Li , Yuting Shen , Zixi Wang , Kun Yin , Xinyao Li , Jian Li , Zijun Zhou
The construction of aza-3D frameworks has emerged as a pivotal strategy in drug discovery, owing to their ability to mimic heteroarene bioisosteres. In this study, we introduce a novel strategy that employs an octahedral rhodium complex as an efficient Lewis acid catalyst for the cycloaddition reaction between bicyclo[1.1.0]butanes and N,N′-cyclic azomethine imines, yielding versatile azabicyclo[3.1.1]heptane derivatives. The reaction proceeds smoothly with a broad substrate scope, achieving yields of up to 98% in 27 examples. The synthetic feasibility of this cycloaddition reaction was demonstrated through a scaled-up reaction using only 2 mol% catalyst loading, followed by further transformations of the cyclized BCHeps product. Control experiments together with DFT calculations illustrated the detailed reaction pathway. Additionally, we have developed an enantioselective version of this reaction using a chiral-at-Rhodium catalyst (up to 91% ee).
{"title":"Rhodium-catalyzed cycloaddition of bicyclo[1.1.0]butanes with N,N′-cyclic azomethine imines: en route to fused diaza-3D scaffolds","authors":"Tianlei Du , Qiujie Qin , Jin Li , Yuting Shen , Zixi Wang , Kun Yin , Xinyao Li , Jian Li , Zijun Zhou","doi":"10.1039/d5qo01147g","DOIUrl":"10.1039/d5qo01147g","url":null,"abstract":"<div><div>The construction of aza-3D frameworks has emerged as a pivotal strategy in drug discovery, owing to their ability to mimic heteroarene bioisosteres. In this study, we introduce a novel strategy that employs an octahedral rhodium complex as an efficient Lewis acid catalyst for the cycloaddition reaction between bicyclo[1.1.0]butanes and <em>N</em>,<em>N</em>′-cyclic azomethine imines, yielding versatile azabicyclo[3.1.1]heptane derivatives. The reaction proceeds smoothly with a broad substrate scope, achieving yields of up to 98% in 27 examples. The synthetic feasibility of this cycloaddition reaction was demonstrated through a scaled-up reaction using only 2 mol% catalyst loading, followed by further transformations of the cyclized BCHeps product. Control experiments together with DFT calculations illustrated the detailed reaction pathway. Additionally, we have developed an enantioselective version of this reaction using a chiral-at-Rhodium catalyst (up to 91% ee).</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 24","pages":"Pages 6834-6840"},"PeriodicalIF":0.0,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145068164","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}
Jinwoo Lee , Ramachandra Reddy Putta , Junhwa Hong , Seung Hyun Choi , Honghui Lee , Seok Beom Lee , Suckchang Hong
Organic azides and alcohols were harnessed in a transition metal-free, base-mediated transfer hydrogenation system, which offers an efficient synthetic route to secondary amines. In the presence of KOtBu, aryl azides underwent hydrogen transfer with alcohols to produce secondary amines in high yields. The method features a broad substrate scope, gram-scale applicability, and straightforward experimental setup. Furthermore, N-heterocycles such as quinoxalines and quinolines were synthesized under similar reaction conditions. Mechanistic studies demonstrated that both alcohols and KOtBu were essential for facilitating hydrogen transfer to azides. The exclusion of a radical pathway, confirmation of alcohol as the reductant, and deuterium labeling experiments provided key insights into the reaction mechanism. DFT calculations revealed that the reduction of azides proceeded through a six-membered cyclic transition state, resembling the mechanism proposed for the Meerwein–Ponndorf–Verley (MPV) reduction. Notably, the potassium cation stabilized the transition state by interacting with both the aryl group and the nitrogen atom of the aryl azide.
有机叠氮化物和醇在无过渡金属、碱介导的转移加氢体系中被利用，这为合成仲胺提供了一种有效的途径。在KO - t - Bu存在下，芳基叠氮化物与醇发生氢转移，高产出仲胺。该方法具有广泛的衬底范围，克级适用性和简单的实验设置。此外，在相似的反应条件下合成了n -杂环化合物，如喹诺啉类和喹啉类。机理研究表明，醇和KO - t - Bu都是促进氢向叠氮化物转移所必需的。排除自由基途径，确认醇作为还原剂，以及氘标记实验提供了对反应机制的关键见解。DFT计算表明叠氮化物的还原是通过六元循环过渡态进行的，类似于Meerwein-Ponndorf-Verley （MPV）还原的机制。值得注意的是，钾阳离子通过与芳基和芳基叠氮化物的氮原子相互作用来稳定过渡态。
{"title":"Transition metal-free transfer hydrogenation of aryl azides with alcohols: direct synthesis of secondary amines and N-heterocycles","authors":"Jinwoo Lee , Ramachandra Reddy Putta , Junhwa Hong , Seung Hyun Choi , Honghui Lee , Seok Beom Lee , Suckchang Hong","doi":"10.1039/d5qo01070e","DOIUrl":"10.1039/d5qo01070e","url":null,"abstract":"<div><div>Organic azides and alcohols were harnessed in a transition metal-free, base-mediated transfer hydrogenation system, which offers an efficient synthetic route to secondary amines. In the presence of KO<sup><em>t</em></sup>Bu, aryl azides underwent hydrogen transfer with alcohols to produce secondary amines in high yields. The method features a broad substrate scope, gram-scale applicability, and straightforward experimental setup. Furthermore, N-heterocycles such as quinoxalines and quinolines were synthesized under similar reaction conditions. Mechanistic studies demonstrated that both alcohols and KO<sup><em>t</em></sup>Bu were essential for facilitating hydrogen transfer to azides. The exclusion of a radical pathway, confirmation of alcohol as the reductant, and deuterium labeling experiments provided key insights into the reaction mechanism. DFT calculations revealed that the reduction of azides proceeded through a six-membered cyclic transition state, resembling the mechanism proposed for the Meerwein–Ponndorf–Verley (MPV) reduction. Notably, the potassium cation stabilized the transition state by interacting with both the aryl group and the nitrogen atom of the aryl azide.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 24","pages":"Pages 7026-7034"},"PeriodicalIF":0.0,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145133461","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}
Phung Phan Huyen Quyen , Nina Hagmeyer , Thanh Huyen Vuong , Adrian Prudlik , Robert Francke , Benjamin Dietzek-Ivanšić , Esteban Mejía
Inspired by the synthetic potential of organic photoredox catalysts, we synthesised and characterised a series of 5,10-dihydrophenazine derivatives that bear heterocycles as electron-withdrawing groups. Upon exploring their photocatalytic behaviour, we discovered that these compounds exhibit Janus-type reactivity, enabling both oxidative C(sp3)–H cyanation and reductive aryl halide cleavage. We investigated their photophysical and electrochemical properties through cyclic voltammetry (CV), transient absorption spectroscopy (TA) and UV-Vis spectroelectrochemistry (SEC). Time-resolved UV-Vis spectroscopy and electron paramagnetic resonance (EPR) provided valuable information on excited-state dynamics and radical cation formation. This revealed that the catalysts act as effective reductants for C(sp2)–I bond cleavage, generating aryl radicals. Furthermore, the excited-state radical cation facilitates the oxidative C(sp3)–H cyanation of tertiary amines. Our mechanistic studies confirm the dual redox nature of these catalysts, thereby expanding the utility of 5,10-dihydrophenazine derivatives in photoredox catalysis.
{"title":"Janus-type photo-redox properties and catalytic applications of 5,10-dihydrophenazine derivatives","authors":"Phung Phan Huyen Quyen , Nina Hagmeyer , Thanh Huyen Vuong , Adrian Prudlik , Robert Francke , Benjamin Dietzek-Ivanšić , Esteban Mejía","doi":"10.1039/d5qo01348h","DOIUrl":"10.1039/d5qo01348h","url":null,"abstract":"<div><div>Inspired by the synthetic potential of organic photoredox catalysts, we synthesised and characterised a series of 5,10-dihydrophenazine derivatives that bear heterocycles as electron-withdrawing groups. Upon exploring their photocatalytic behaviour, we discovered that these compounds exhibit Janus-type reactivity, enabling both oxidative C(sp<sup>3</sup>)–H cyanation and reductive aryl halide cleavage. We investigated their photophysical and electrochemical properties through cyclic voltammetry (CV), transient absorption spectroscopy (TA) and UV-Vis spectroelectrochemistry (SEC). Time-resolved UV-Vis spectroscopy and electron paramagnetic resonance (EPR) provided valuable information on excited-state dynamics and radical cation formation. This revealed that the catalysts act as effective reductants for C(sp<sup>2</sup>)–I bond cleavage, generating aryl radicals. Furthermore, the excited-state radical cation facilitates the oxidative C(sp<sup>3</sup>)–H cyanation of tertiary amines. Our mechanistic studies confirm the dual redox nature of these catalysts, thereby expanding the utility of 5,10-dihydrophenazine derivatives in photoredox catalysis.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 24","pages":"Pages 6798-6819"},"PeriodicalIF":0.0,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145478462","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}
Anna S. Rumyantseva , Konstantin A. Lyssenko , Tatiana V. Magdesieva
An unusual reactivity channel of semisquaraines has been disclosed, yielding a novel type of oxocarbon derivative via a facile synthetic procedure. The compound exhibits extremely rare “double” redox-ambipolarity (i.e., strong stabilization of both mono- and di-oppositely charged ionic states) sustained by a relatively small conjugated system. The remarkable “atom-economic” structure of the oxocarbon provides two orthogonal channels for charge/spin delocalization that are combined via the central 6-membered ring. The ring may be either in an aromatic or in a quinoidal state, thereby controlling charge redistribution and ensuring stabilization of five redox states. The radical cation shows no destruction in 24 h; the half-life of the radical anion is 2.5 h at r.t. in dichlorobenzene. The stability of multiple redox states, in combination with intensive UV-vis-NIR absorption, yields pronounced electrochromic behaviour that makes the novel oxocarbon derivative potentially interesting for application in electrochromic displays, in photovoltaics, as well as having potential as a redox indicator, e.g., for sensing metal ions (as shown experimentally). In the crystal state, the compound demonstrates high thermal stability and is prone to form a π-stacked 1D supramolecular structure.
{"title":"A novel member of the benzo-annulated oxocarbon family","authors":"Anna S. Rumyantseva , Konstantin A. Lyssenko , Tatiana V. Magdesieva","doi":"10.1039/d5qo01058f","DOIUrl":"10.1039/d5qo01058f","url":null,"abstract":"<div><div>An unusual reactivity channel of semisquaraines has been disclosed, yielding a novel type of oxocarbon derivative <em>via</em> a facile synthetic procedure. The compound exhibits extremely rare “double” redox-ambipolarity (<em>i.e.</em>, strong stabilization of both mono- and di-oppositely charged ionic states) sustained by a relatively small conjugated system. The remarkable “atom-economic” structure of the oxocarbon provides two orthogonal channels for charge/spin delocalization that are combined <em>via</em> the central 6-membered ring. The ring may be either in an aromatic or in a quinoidal state, thereby controlling charge redistribution and ensuring stabilization of five redox states. The radical cation shows no destruction in 24 h; the half-life of the radical anion is 2.5 h at r.t. in dichlorobenzene. The stability of multiple redox states, in combination with intensive UV-vis-NIR absorption, yields pronounced electrochromic behaviour that makes the novel oxocarbon derivative potentially interesting for application in electrochromic displays, in photovoltaics, as well as having potential as a redox indicator, <em>e.g.</em>, for sensing metal ions (as shown experimentally). In the crystal state, the compound demonstrates high thermal stability and is prone to form a π-stacked 1D supramolecular structure.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 24","pages":"Pages 7035-7042"},"PeriodicalIF":0.0,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145077882","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}
Jiawen Wu , Siying Zhao , Xiu-tian-feng E , Junfeng Wang , Zhonghua Xia
The growing demand for aryl azides in diverse fields has spurred significant advances in their synthetic methodologies. Herein, we report a gold-catalyzed C–N3 cross-coupling reaction enabled by ligand-supported Au(i)/Au(iii) redox catalysis. This method employs trimethylsilyl azide (TMSN3) as a practical azide source to efficiently convert simple aryl iodides into the corresponding aryl azides. Key features of this transformation include broad substrate scope and compatibility with post-functionalization strategies. Mechanistic insights derived from combined experimental studies, computational analyses, and X-ray crystallography of two key intermediates reveal that oxidative addition and ligand exchange/azide transfer proceed smoothly, whereas thermal or photoinduced conditions facilitate the challenging reductive elimination of the Au(iii)–azide intermediate.
{"title":"Gold-catalyzed azidation with TMSN3 and mechanistic studies","authors":"Jiawen Wu , Siying Zhao , Xiu-tian-feng E , Junfeng Wang , Zhonghua Xia","doi":"10.1039/d5qo01091h","DOIUrl":"10.1039/d5qo01091h","url":null,"abstract":"<div><div>The growing demand for aryl azides in diverse fields has spurred significant advances in their synthetic methodologies. Herein, we report a gold-catalyzed C–N<sub>3</sub> cross-coupling reaction enabled by ligand-supported Au(<span>i</span>)/Au(<span>iii</span>) redox catalysis. This method employs trimethylsilyl azide (TMSN<sub>3</sub>) as a practical azide source to efficiently convert simple aryl iodides into the corresponding aryl azides. Key features of this transformation include broad substrate scope and compatibility with post-functionalization strategies. Mechanistic insights derived from combined experimental studies, computational analyses, and X-ray crystallography of two key intermediates reveal that oxidative addition and ligand exchange/azide transfer proceed smoothly, whereas thermal or photoinduced conditions facilitate the challenging reductive elimination of the Au(<span>iii</span>)–azide intermediate.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 24","pages":"Pages 6961-6965"},"PeriodicalIF":0.0,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145067780","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}
As a versatile synthetic transformation, the dicarbofunctionalization of 1,3-butadiene enables the rapid assembly of structurally diverse allylic scaffolds. Herein, the selective 1,4-dicarbofunctionalization of 1,3-butadiene with organobromides (alkyl and aryl bromides) and malononitrile nucleophiles has been developed using a photoinduced Pd-catalyzed three-component coupling strategy. This process relies on photoexcited Pd(0) activation of both substrates through a single-electron transfer (SET) process, accommodating alkyl and aryl radicals of contrasting electronic character through precisely optimized reaction conditions. Under mild conditions, the protocol furnishes 74 functionalized malononitrile derivatives in high yields (up to 88%) and excellent regioselectivity (>20 : 1 rr), highlighting its broad scope and efficiency.
{"title":"Visible light-promoted Pd-catalyzed regioselective 1,4-dicarbofunctionalization of 1,3-butadiene with unactivated bromides and malononitriles","authors":"Mostafa Sayed , Xiao-Yun Ruan , Chenxi Wu , Ji-Feng Bai","doi":"10.1039/d5qo01117e","DOIUrl":"10.1039/d5qo01117e","url":null,"abstract":"<div><div>As a versatile synthetic transformation, the dicarbofunctionalization of 1,3-butadiene enables the rapid assembly of structurally diverse allylic scaffolds. Herein, the selective 1,4-dicarbofunctionalization of 1,3-butadiene with organobromides (alkyl and aryl bromides) and malononitrile nucleophiles has been developed using a photoinduced Pd-catalyzed three-component coupling strategy. This process relies on photoexcited Pd(0) activation of both substrates through a single-electron transfer (SET) process, accommodating alkyl and aryl radicals of contrasting electronic character through precisely optimized reaction conditions. Under mild conditions, the protocol furnishes 74 functionalized malononitrile derivatives in high yields (up to 88%) and excellent regioselectivity (>20 : 1 rr), highlighting its broad scope and efficiency.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 24","pages":"Pages 6944-6952"},"PeriodicalIF":0.0,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145084336","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}
A catalyst and additive-free nucleophilic addition of sulfoxonium ylides to hypervalent iodine diazo reagents as N-terminal electrophiles has been developed. The reaction not only leads to a facile access to highly functionalized hydrazones but also significantly advances the understanding of hitherto unexplored terminal N-electrophilicity in HIDCs. The operational simplicity, wide substrate scope, high product yields and mild conditions are notable features of the methodology.
{"title":"Nucleophilic addition of sulfoxonium ylides to hypervalent iodine diazo compounds as N-terminal electrophiles: direct access to novel functionalized hydrazones","authors":"Varun Anand , Ruchir Kant , Namrata Rastogi","doi":"10.1039/d5qo00885a","DOIUrl":"10.1039/d5qo00885a","url":null,"abstract":"<div><div>A catalyst and additive-free nucleophilic addition of sulfoxonium ylides to hypervalent iodine diazo reagents as N-terminal electrophiles has been developed. The reaction not only leads to a facile access to highly functionalized hydrazones but also significantly advances the understanding of hitherto unexplored terminal <em>N</em>-electrophilicity in HIDCs. The operational simplicity, wide substrate scope, high product yields and mild conditions are notable features of the methodology.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 24","pages":"Pages 6879-6884"},"PeriodicalIF":0.0,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145059785","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}
Yufei Xia , Wang Sun , Qiao Yang , Li Jiang , Ying Wang , Yunbin Hu , Fengkun Chen
Negatively curved chiral nanographenes (NGs) have recently garnered significant interest as aesthetically unique carbon allotropes with unique topologies and extraordinary physicochemical properties. However, the construction of such π-systems bearing multiple heptagons and helical chirality remains challenging. Herein, we reported the successful preparation of a saddle-shaped chiral NG incorporating two heptagons and a thia[6]helicene unit, along with a triple thia[6]helicene , by controlled Scholl reactions. Single crystal X-ray diffraction analysis revealed that adopted a highly distorted architecture with a pronounced torsional angle of 30.3° with regard to the central benzene ring. The formation of two additional heptagons in resulted in red-shifted absorption and emission, as well as enhanced fluorescence quantum yield compared to . The oxidation of the sulfur atoms in compounds and to their corresponding sulfone-incorporated analogues, and , respectively, was found to be an efficient approach to modulate the electronic and electrochemical properties. Furthermore, the relatively high racemization barriers of these compounds enabled their chiral resolution and facilitated the characterization of their chiroptical properties.
{"title":"Saddle-shaped chiral nanographenes embedded with dipleiadiene and thia[6]helicene units","authors":"Yufei Xia , Wang Sun , Qiao Yang , Li Jiang , Ying Wang , Yunbin Hu , Fengkun Chen","doi":"10.1039/d5qo01263e","DOIUrl":"10.1039/d5qo01263e","url":null,"abstract":"<div><div>Negatively curved chiral nanographenes (NGs) have recently garnered significant interest as aesthetically unique carbon allotropes with unique topologies and extraordinary physicochemical properties. However, the construction of such π-systems bearing multiple heptagons and helical chirality remains challenging. Herein, we reported the successful preparation of a saddle-shaped chiral NG incorporating two heptagons and a thia[6]helicene unit, along with a triple thia[6]helicene , by controlled Scholl reactions. Single crystal X-ray diffraction analysis revealed that adopted a highly distorted architecture with a pronounced torsional angle of 30.3° with regard to the central benzene ring. The formation of two additional heptagons in resulted in red-shifted absorption and emission, as well as enhanced fluorescence quantum yield compared to . The oxidation of the sulfur atoms in compounds and to their corresponding sulfone-incorporated analogues, and , respectively, was found to be an efficient approach to modulate the electronic and electrochemical properties. Furthermore, the relatively high racemization barriers of these compounds enabled their chiral resolution and facilitated the characterization of their chiroptical properties.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 24","pages":"Pages 6980-6988"},"PeriodicalIF":0.0,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145116517","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}
The enantioselective organocatalytic α-chlorination of aldehydes using electrochemistry to activate the enamine intermediate through a SOMO strategy was investigated. Based on mechanistic insights, an improved procedure was developed that directly employs CuCl2 in the electrochemical reaction. Under the optimized setup (potentiostatic conditions of 1 V, glassy-carbon electrodes, and a 0.2 M solution of LiClO4), in the presence of catalytic amounts of a chiral imidazolidinone organocatalyst, the aldehyde reacts with copper chloride(ii) and leads to the formation of the corresponding α-chlorinated aldehydes in high yields with high enantioselectivities (up to 97% ee). Thanks to the electrochemical approach, stoichiometric amounts of chemical oxidants were successfully replaced by electrons, enabling a more sustainable and efficient catalytic stereoselective reaction. In addition, the transformation was successfully translated to a continuous flow process, which significantly enhanced productivity and reduced the reaction time to just 1.73 minutes, and the reaction was also performed on a gram scale.
{"title":"Enantioselective organocatalytic electrochemical α-chlorination of aldehydes","authors":"Stefano Andolina , Alessandra Puglisi , Sergio Rossi , Fabrizio Medici , Maurizio Benaglia","doi":"10.1039/d5qo01249j","DOIUrl":"10.1039/d5qo01249j","url":null,"abstract":"<div><div>The enantioselective organocatalytic α-chlorination of aldehydes using electrochemistry to activate the enamine intermediate through a SOMO strategy was investigated. Based on mechanistic insights, an improved procedure was developed that directly employs CuCl<sub>2</sub> in the electrochemical reaction. Under the optimized setup (potentiostatic conditions of 1 V, glassy-carbon electrodes, and a 0.2 M solution of LiClO<sub>4</sub>), in the presence of catalytic amounts of a chiral imidazolidinone organocatalyst, the aldehyde reacts with copper chloride(<span>ii</span>) and leads to the formation of the corresponding α-chlorinated aldehydes in high yields with high enantioselectivities (up to 97% ee). Thanks to the electrochemical approach, stoichiometric amounts of chemical oxidants were successfully replaced by electrons, enabling a more sustainable and efficient catalytic stereoselective reaction. In addition, the transformation was successfully translated to a continuous flow process, which significantly enhanced productivity and reduced the reaction time to just 1.73 minutes, and the reaction was also performed on a gram scale.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 24","pages":"Pages 7055-7063"},"PeriodicalIF":0.0,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145141108","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}
An electrochemical three-component reaction involving isocyanides, sulfonamides and disulfides was developed, using nBu4NI as a redox catalyst and electrolyte. A rare N-to-N [1,3]-H shift was observed in this transformation. This method represents a highly efficient and cost-effective approach for the synthesis of N-sulfonyl isothioureas.
{"title":"Clean and economic synthesis of N-sulfonyl isothioureas from isocyanides, sulfonamides and disulfides","authors":"Changping Xun , Zhibin Nong , Kun Hu , Wenfeng Lv , Jiajun Zhao , Ziqiong Yin , Jialu Lv , Feng Jiang , Qing-Wen Gui","doi":"10.1039/d5qo00867k","DOIUrl":"10.1039/d5qo00867k","url":null,"abstract":"<div><div>An electrochemical three-component reaction involving isocyanides, sulfonamides and disulfides was developed, using <sup><em>n</em></sup>Bu<sub>4</sub>NI as a redox catalyst and electrolyte. A rare N-to-N [1,3]-H shift was observed in this transformation. This method represents a highly efficient and cost-effective approach for the synthesis of <em>N</em>-sulfonyl isothioureas.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 24","pages":"Pages 6873-6878"},"PeriodicalIF":0.0,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144911121","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}
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