Shi-Zheng Liu , Wen-Heng Liu , Yaotai Deng , Qiang Li , Ming-Yu Dou , Yu Cui , Jian-Min Dou
A metal-free, HBF4-mediated alcoholysis of amides under relatively mild conditions is reported. This operationally simple process provides a new route to amide–ester bond conversion with excellent chemoselectivity. In particular, a wide range of primary, secondary and tertiary amides, including the challenging thioamides, can be esterified in very high yields. In addition, this transformation does not require the use of additional solvent, and many products can be obtained by washing with water.
{"title":"HBF4-mediated direct alcoholysis of amides under mild conditions†","authors":"Shi-Zheng Liu , Wen-Heng Liu , Yaotai Deng , Qiang Li , Ming-Yu Dou , Yu Cui , Jian-Min Dou","doi":"10.1039/d5qo00603a","DOIUrl":"10.1039/d5qo00603a","url":null,"abstract":"<div><div>A metal-free, HBF<sub>4</sub>-mediated alcoholysis of amides under relatively mild conditions is reported. This operationally simple process provides a new route to amide–ester bond conversion with excellent chemoselectivity. In particular, a wide range of primary, secondary and tertiary amides, including the challenging thioamides, can be esterified in very high yields. In addition, this transformation does not require the use of additional solvent, and many products can be obtained by washing with water.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5438-5444"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144229280","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}
Lin Wan , Yude Ji , Zikang Ma , Chengguo Yan , Weifan Wang , Gang Zhang
Planar and positively curved carbonyl-bridged triphenylamine derivatives with five- and six-membered rings around the central nitrogen atom have been extensively studied. However, the incorporation of seven-membered rings to form negatively curved carbonyl-bridged triphenylamine derivatives is still scarce. Herein, we report the synthesis of a negatively curved carbonyl-bridged triphenylamine compound bearing double hexagonal rings and a heptagonal ring around the central nitrogen atom. The peripheral double bond of the heptagonal ring can be oxidized to form an adjacent diketone compound with room temperature phosphorescence. Naphthalene and quinoxaline units can be fused to the seven-membered ring to give saddle-shaped derivatives, which can assemble with C60 in a 1 : 1 ratio in toluene, with different binding constants depending on the fused units.
{"title":"A negatively curved carbonyl-bridged triphenylamine†","authors":"Lin Wan , Yude Ji , Zikang Ma , Chengguo Yan , Weifan Wang , Gang Zhang","doi":"10.1039/d5qo00794a","DOIUrl":"10.1039/d5qo00794a","url":null,"abstract":"<div><div>Planar and positively curved carbonyl-bridged triphenylamine derivatives with five- and six-membered rings around the central nitrogen atom have been extensively studied. However, the incorporation of seven-membered rings to form negatively curved carbonyl-bridged triphenylamine derivatives is still scarce. Herein, we report the synthesis of a negatively curved carbonyl-bridged triphenylamine compound bearing double hexagonal rings and a heptagonal ring around the central nitrogen atom. The peripheral double bond of the heptagonal ring can be oxidized to form an adjacent diketone compound with room temperature phosphorescence. Naphthalene and quinoxaline units can be fused to the seven-membered ring to give saddle-shaped derivatives, which can assemble with C<sub>60</sub> in a 1 : 1 ratio in toluene, with different binding constants depending on the fused units.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5533-5539"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144260600","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}
Shuai Qiu , Yuexia Dong , Wan Xu , Sheng Zhang , Chunli Li , Hua Wang
Three new thiophene/selenophene-based S/Se-[7]helicenes were efficiently synthesized via intermolecular McMurry and oxidative photocyclization reactions. Their helical structures were confirmed through single-crystal analysis. Additionally, these [7]helicenes exhibited notable circularly polarized phosphorescence at 77 K. Theoretical calculations show that both intersystem crossing channels and spin–orbit coupling constants are increased due to the heavy atom effect.
{"title":"Sulfur/selenium atom-incorporated hetero[7]helicenes for low-temperature circularly polarized phosphorescence†","authors":"Shuai Qiu , Yuexia Dong , Wan Xu , Sheng Zhang , Chunli Li , Hua Wang","doi":"10.1039/d5qo00790a","DOIUrl":"10.1039/d5qo00790a","url":null,"abstract":"<div><div>Three new thiophene/selenophene-based S/Se-[7]helicenes were efficiently synthesized <em>via</em> intermolecular McMurry and oxidative photocyclization reactions. Their helical structures were confirmed through single-crystal analysis. Additionally, these [7]helicenes exhibited notable circularly polarized phosphorescence at 77 K. Theoretical calculations show that both intersystem crossing channels and spin–orbit coupling constants are increased due to the heavy atom effect.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5559-5565"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144341354","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}
Liangwei Zhu , Lin Zhang , Jian Zhang , Peigen Wang , Ruopeng Bai , Zhonglin Tao
The asymmetric α-alkylation of simple ketones with unactivated alkyl halides remains a longstanding challenge in organic synthesis. Herein, we report a dinickel-catalyzed asymmetric α-alkylation of cyclic ketones using unactivated alkyl halides as alkylating agents. This methodology accommodates a broad range of substrates, including benzo-fused cyclic ketones, α-aryl and α-alkyl cyclic ketones, and diverse alkyl halides, enabling the construction of chiral ketones with α-quaternary centers with high regio- and enantioselectivity. Mechanistic studies, combining experimental and computational approaches, reveal that this transformation proceeds via a redox-neutral SN2 pathway catalyzed by nickel(i) species instead of the commonly observed Ni(ii) salt. The unique bimetallic ligand framework plays a dual role: (1) stabilizing adjacent dinickel(i) centers through halogen-bridging interactions, thereby enabling the formation of a highly nucleophilic nickel(i) enolate, and (2) providing a chiral pocket to control the stereochemistry of the reaction.
{"title":"Dinickel-catalyzed regio- and enantioselective α-alkylation of cyclic ketones with unactivated alkyl halides†","authors":"Liangwei Zhu , Lin Zhang , Jian Zhang , Peigen Wang , Ruopeng Bai , Zhonglin Tao","doi":"10.1039/d5qo00448a","DOIUrl":"10.1039/d5qo00448a","url":null,"abstract":"<div><div>The asymmetric α-alkylation of simple ketones with unactivated alkyl halides remains a longstanding challenge in organic synthesis. Herein, we report a dinickel-catalyzed asymmetric α-alkylation of cyclic ketones using unactivated alkyl halides as alkylating agents. This methodology accommodates a broad range of substrates, including benzo-fused cyclic ketones, α-aryl and α-alkyl cyclic ketones, and diverse alkyl halides, enabling the construction of chiral ketones with α-quaternary centers with high regio- and enantioselectivity. Mechanistic studies, combining experimental and computational approaches, reveal that this transformation proceeds <em>via</em> a redox-neutral S<sub>N</sub>2 pathway catalyzed by nickel(<span>i</span>) species instead of the commonly observed Ni(<span>ii</span>) salt. The unique bimetallic ligand framework plays a dual role: (1) stabilizing adjacent dinickel(<span>i</span>) centers through halogen-bridging interactions, thereby enabling the formation of a highly nucleophilic nickel(<span>i</span>) enolate, and (2) providing a chiral pocket to control the stereochemistry of the reaction.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5421-5429"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144201547","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}
Guanghu Tong , Long V. Nguyen , Timothy F. Jamison
Nagelamide C (), a dimeric pyrrole–imidazole alkaloid, exhibits antimicrobial and antibacterial activities. We demonstrate herein the first total synthesis of nagelamide C. This concise work was enabled by a series of significant transformations featuring: an imidazole benzylic Wittig olefination, a site selective bromination, and a regioselective trans-hydrostannylation/Stille coupling to construct a unique trisubstituted olefin. In addition, we show the original 13C NMR data of nagelamide C to be in error and revise the data.
{"title":"Total synthesis and 13C NMR revision of nagelamide C†","authors":"Guanghu Tong , Long V. Nguyen , Timothy F. Jamison","doi":"10.1039/d5qo00721f","DOIUrl":"10.1039/d5qo00721f","url":null,"abstract":"<div><div>Nagelamide C (), a dimeric pyrrole–imidazole alkaloid, exhibits antimicrobial and antibacterial activities. We demonstrate herein the first total synthesis of nagelamide C. This concise work was enabled by a series of significant transformations featuring: an imidazole benzylic Wittig olefination, a site selective bromination, and a regioselective <em>trans</em>-hydrostannylation/Stille coupling to construct a unique trisubstituted olefin. In addition, we show the original <sup>13</sup>C NMR data of nagelamide C to be in error and revise the data.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5453-5458"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144219101","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}
Boron and nitrogen/oxygen-based multi-resonance thermally activated delayed fluorescence (MR-TADF) emitters represent cutting-edge OLED technology in both academic and industrial research, demonstrating high color purity and power efficiency. However, the advancement of these emitters is somewhat constrained due to limited synthetic methodologies and low yields of the emitters and their respective precursors. Therefore, comprehensive knowledge of synthetic approaches is necessary, particularly concerning the precursors for improved molecular development. Most precursors for the final emitter are synthesized by forming C–C/C–X bonds, involving palladium-based catalysts and additives as crucial reagents. In this review, we thoroughly discuss the synthetic approaches used to prepare the intermediates with the palladium catalyst alongside various ligands, along with most of the recent reports. We also outline the general criteria for selecting the Pd catalyst and ligand, their respective molar equivalents, and the corresponding yields.
{"title":"Crucial role of palladium(0/ii) catalysts in the synthesis of multi-resonance thermally activated delayed fluorescence emitters†","authors":"Ajeet Chandra , Paramasivam Palanisamy , Aradhya Rajput , Jang Hyuk Kwon","doi":"10.1039/d5qo00522a","DOIUrl":"10.1039/d5qo00522a","url":null,"abstract":"<div><div>Boron and nitrogen/oxygen-based multi-resonance thermally activated delayed fluorescence (MR-TADF) emitters represent cutting-edge OLED technology in both academic and industrial research, demonstrating high color purity and power efficiency. However, the advancement of these emitters is somewhat constrained due to limited synthetic methodologies and low yields of the emitters and their respective precursors. Therefore, comprehensive knowledge of synthetic approaches is necessary, particularly concerning the precursors for improved molecular development. Most precursors for the final emitter are synthesized by forming C–C/C–X bonds, involving palladium-based catalysts and additives as crucial reagents. In this review, we thoroughly discuss the synthetic approaches used to prepare the intermediates with the palladium catalyst alongside various ligands, along with most of the recent reports. We also outline the general criteria for selecting the Pd catalyst and ligand, their respective molar equivalents, and the corresponding yields.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5644-5682"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144177136","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}
Xiaoning Yang , Shuyan Wu , Jiayi Wang , Yanqing Peng , Gonghua Song
Benzoxaboroles and benzodiazaborines are pivotal in medicinal chemistry due to their unique biological activities and potential as therapeutic agents. Herein, we present a room-temperature, nickel-catalyzed borylation protocol for their efficient synthesis. Utilizing an inexpensive nickel catalyst system, this method provides a facile synthetic method for a wide range of target compounds. This cost-effective approach offers a sustainable alternative to traditional palladium-based methods, aligning with green chemistry principles by reducing energy input and enhancing reaction efficiency. In addition to expanding the range of boronic acid derivatives, the developed methodology holds significant promise for advancing applications in drug discovery.
{"title":"Room-temperature nickel-catalyzed borylation/cyclization for the synthesis of benzoxaboroles and benzodiazaborines†","authors":"Xiaoning Yang , Shuyan Wu , Jiayi Wang , Yanqing Peng , Gonghua Song","doi":"10.1039/d5qo00728c","DOIUrl":"10.1039/d5qo00728c","url":null,"abstract":"<div><div>Benzoxaboroles and benzodiazaborines are pivotal in medicinal chemistry due to their unique biological activities and potential as therapeutic agents. Herein, we present a room-temperature, nickel-catalyzed borylation protocol for their efficient synthesis. Utilizing an inexpensive nickel catalyst system, this method provides a facile synthetic method for a wide range of target compounds. This cost-effective approach offers a sustainable alternative to traditional palladium-based methods, aligning with green chemistry principles by reducing energy input and enhancing reaction efficiency. In addition to expanding the range of boronic acid derivatives, the developed methodology holds significant promise for advancing applications in drug discovery.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5547-5552"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144278650","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}
Propargyl moieties are important structural units that are ubiquitous in numerous natural products and pharmaceutical molecules. Due to the high reaction barrier, copper-catalyzed enantioselective propargylation with propargylic alcohols has not been reported so far. Herein, we describe the first example of copper-catalyzed asymmetric propargylic substitution reactions of propargylic alcohols. The N,N,P-ligand functions as a bifunctional reagent, acting as a base catalyst to promote the esterification of propargylic alcohols and serving as a tridentate ligand to coordinate with copper salts, thereby forming a catalyst that activates propargylic esters. The methodology proceeds under mild reaction conditions and is tolerant to N-, C-, and O-nucleophiles, generating propargylic substitution products in good to excellent yields with high enantioselectivities (up to 95% yield, 97% ee). This methodology might open a new avenue for designing copper-catalyzed propargylic substitution reactions with propargylic alcohols.
{"title":"Chiral bifunctional N,N,P-ligand-enabled cooperative Cu catalysis: one-pot two-step propargylic substitution of propargylic alcohols†","authors":"Ruinan Zhao , Zihao Wang , Ting Fang , Chibin Zhang , Lijun Tang , Cuiju Zhu , Hao Xu","doi":"10.1039/d5qo00595g","DOIUrl":"10.1039/d5qo00595g","url":null,"abstract":"<div><div>Propargyl moieties are important structural units that are ubiquitous in numerous natural products and pharmaceutical molecules. Due to the high reaction barrier, copper-catalyzed enantioselective propargylation with propargylic alcohols has not been reported so far. Herein, we describe the first example of copper-catalyzed asymmetric propargylic substitution reactions of propargylic alcohols. The <em>N</em>,<em>N</em>,<em>P</em>-ligand functions as a bifunctional reagent, acting as a base catalyst to promote the esterification of propargylic alcohols and serving as a tridentate ligand to coordinate with copper salts, thereby forming a catalyst that activates propargylic esters. The methodology proceeds under mild reaction conditions and is tolerant to <em>N</em>-, <em>C</em>-, and <em>O</em>-nucleophiles, generating propargylic substitution products in good to excellent yields with high enantioselectivities (up to 95% yield, 97% ee). This methodology might open a new avenue for designing copper-catalyzed propargylic substitution reactions with propargylic alcohols.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5511-5518"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144219153","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}
Jiahao Gu , Zhenyang Wan , Yuhong Lu , Xiangmin Tian , Ziyue Zeng , Dailin Zhuang , Ziyuan Li
A remote activating strategy enabled (RASE) π-bond migratory dealkylative C(sp3)–N and C(sp2)–N coupling with 2-alkoxylthiazole through C(sp3)–H and C(sp2)–H cleavage has been achieved under mild conditions, affording N-benzyl or N-phenyl thiazol-2(3H)-ones, respectively. N-Fluorobenzenesulfonimide (NFSI) serves as a crucial bifunctional domino reagent: it not only generates a nitrogen-centred radical that initiates N–C or N–N radical relay, thereby providing the electrophile coupling partner, but also produces N-hydrobenzenesulfonimide (NHSI), a key carbocation scavenger that triggers the π-bond migratory dealkylation of 2-alkoxylthiazole to yield the nucleophilic thiazol-2(3H)-one coupling partner. A plausible mechanism has been proposed based on the results of mechanistic studies.
{"title":"Remote activating strategy enabled (RASE) π-bond migratory dealkylative C–N coupling utilising N-fluorobenzenesulfonimide (NFSI) as a bifunctional domino reagent†","authors":"Jiahao Gu , Zhenyang Wan , Yuhong Lu , Xiangmin Tian , Ziyue Zeng , Dailin Zhuang , Ziyuan Li","doi":"10.1039/d5qo00480b","DOIUrl":"10.1039/d5qo00480b","url":null,"abstract":"<div><div>A remote activating strategy enabled (RASE) π-bond migratory dealkylative C(sp<sup>3</sup>)–N and C(sp<sup>2</sup>)–N coupling with 2-alkoxylthiazole through C(sp<sup>3</sup>)–H and C(sp<sup>2</sup>)–H cleavage has been achieved under mild conditions, affording <em>N</em>-benzyl or <em>N</em>-phenyl thiazol-2(3<em>H</em>)-ones, respectively. <em>N</em>-Fluorobenzenesulfonimide (NFSI) serves as a crucial bifunctional domino reagent: it not only generates a nitrogen-centred radical that initiates <em>N</em>–<em>C</em> or <em>N</em>–<em>N</em> radical relay, thereby providing the electrophile coupling partner, but also produces <em>N</em>-hydrobenzenesulfonimide (NHSI), a key carbocation scavenger that triggers the π-bond migratory dealkylation of 2-alkoxylthiazole to yield the nucleophilic thiazol-2(3<em>H</em>)-one coupling partner. A plausible mechanism has been proposed based on the results of mechanistic studies.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5472-5483"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144201544","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}
Zhichao Shi , Tingting Fan , Jin-Shun Lin , Weibin Xie , Feng Zhan , Zhe Wang , Qinglu Zuo , Haoran Fu , Xun Zhang , Qiuhua Huang , Yuyang Jiang
Chiral oxazolidines are pivotal structural motifs commonly found in natural products, medicinally important compounds, and chiral ligands. Among various synthetic strategies, the asymmetric formal (3 + 2) annulation of donor–acceptor (D–A) aziridines with dipolarophiles has emerged as a powerful method for constructing enantioenriched five-membered azaheterocycles with potential bioactivity. Herein, we present a Cu(ii)/chiral phosphoric acid (CPA) cooperative catalytic system for the asymmetric intermolecular (3 + 2) cycloaddition of D–A aziridines with aldehydes via C–C bond cleavage. This approach enables the efficient and highly enantioselective synthesis of cis-(2S,5S)-1,3-oxazolidines with excellent atom economy, as well as exceptional chemo-, enantio-, and diastereoselectivities. This novel activation model, distinct from existing catalytic methodologies, serves as a complementary approach that significantly broadens the scope of asymmetric (3 + 2) cycloaddition of D–A aziridines. Moreover, the resulting chiral oxazolidines exhibited significant anti-proliferative activity against various human cancer cell lines, highlighting their potential for further advancement in medicinal chemistry.
{"title":"Cu/chiral phosphoric acid-catalyzed asymmetric (3 + 2) cycloaddition of donor–acceptor aziridines with aldehydes: synthesis of enantioenriched oxazolidines as potential antitumor agents†","authors":"Zhichao Shi , Tingting Fan , Jin-Shun Lin , Weibin Xie , Feng Zhan , Zhe Wang , Qinglu Zuo , Haoran Fu , Xun Zhang , Qiuhua Huang , Yuyang Jiang","doi":"10.1039/d5qo00729a","DOIUrl":"10.1039/d5qo00729a","url":null,"abstract":"<div><div>Chiral oxazolidines are pivotal structural motifs commonly found in natural products, medicinally important compounds, and chiral ligands. Among various synthetic strategies, the asymmetric formal (3 + 2) annulation of donor–acceptor (D–A) aziridines with dipolarophiles has emerged as a powerful method for constructing enantioenriched five-membered azaheterocycles with potential bioactivity. Herein, we present a Cu(<span>ii</span>)/chiral phosphoric acid (CPA) cooperative catalytic system for the asymmetric intermolecular (3 + 2) cycloaddition of D–A aziridines with aldehydes <em>via</em> C–C bond cleavage. This approach enables the efficient and highly enantioselective synthesis of <em>cis</em>-(2<em>S</em>,5<em>S</em>)-1,3-oxazolidines with excellent atom economy, as well as exceptional chemo-, enantio-, and diastereoselectivities. This novel activation model, distinct from existing catalytic methodologies, serves as a complementary approach that significantly broadens the scope of asymmetric (3 + 2) cycloaddition of D–A aziridines. Moreover, the resulting chiral oxazolidines exhibited significant anti-proliferative activity against various human cancer cell lines, highlighting their potential for further advancement in medicinal chemistry.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5573-5581"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144329439","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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