Pub Date : 2025-03-07DOI: 10.1021/acs.orglett.5c00195
Cui Jian, Zhikai Li, Yuyuan Mao, Yilin Zhu, Weijie Yu, Jie Wu, Shaoyu Li
The β-pyridyl amide is a critical scaffold in medical discovery yet lacks efficient synthetic methods. Here, we describe, for the first time, a visible-light-induced, redox-neutral radical cross-coupling reaction involving alkenes, oxamic acids, and cyanopyridines that offers a versatile assembly of β-pyridylamides. This approach features mild reaction conditions, high step efficiency, and substrate breadth, providing a green and efficient strategy for alkene pyridyl-carbamoylation. Achieving this transformation relies on the efficient catalytic system, which adeptly avoids the competing cross-coupling of the nucleophilic carbamoyl radical with the electrophilic pyridyl radical, enabling the three-component radical tandem reaction process with high chemoselectivity.
{"title":"Photocatalytic Pyridyl-carbamoylation of Alkenes for Accessing β-Pyridyl Amides","authors":"Cui Jian, Zhikai Li, Yuyuan Mao, Yilin Zhu, Weijie Yu, Jie Wu, Shaoyu Li","doi":"10.1021/acs.orglett.5c00195","DOIUrl":"https://doi.org/10.1021/acs.orglett.5c00195","url":null,"abstract":"The β-pyridyl amide is a critical scaffold in medical discovery yet lacks efficient synthetic methods. Here, we describe, for the first time, a visible-light-induced, redox-neutral radical cross-coupling reaction involving alkenes, oxamic acids, and cyanopyridines that offers a versatile assembly of β-pyridylamides. This approach features mild reaction conditions, high step efficiency, and substrate breadth, providing a green and efficient strategy for alkene pyridyl-carbamoylation. Achieving this transformation relies on the efficient catalytic system, which adeptly avoids the competing cross-coupling of the nucleophilic carbamoyl radical with the electrophilic pyridyl radical, enabling the three-component radical tandem reaction process with high chemoselectivity.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"27 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143570329","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}
Pub Date : 2025-03-07Epub Date: 2025-02-27DOI: 10.1021/acs.orglett.5c00587
Xiangshuai Du, Guodan Lu, Tao Zhang, Congzhou Wang, Yong Wang, Xiaobing Wan
Under the combined action of trichloroisocyanuric acid (TCCA) and triflic acid (TfOH), tertiary sulfonamides are efficiently activated, leading to the in situ generation of electrophilic sulfonamide salts. These electrophilic salts subsequently undergo nucleophilic substitution by alcohols, resulting in the formation of sulfonate esters under mild conditions. Other advantages of this method include the absence of transition-metal catalysts, broad substrate applicability, and high functional-group tolerance.
{"title":"Nucleophilic Substitution of Tertiary Sulfonamides: Construction of Sulfonate Esters.","authors":"Xiangshuai Du, Guodan Lu, Tao Zhang, Congzhou Wang, Yong Wang, Xiaobing Wan","doi":"10.1021/acs.orglett.5c00587","DOIUrl":"10.1021/acs.orglett.5c00587","url":null,"abstract":"<p><p>Under the combined action of trichloroisocyanuric acid (TCCA) and triflic acid (TfOH), tertiary sulfonamides are efficiently activated, leading to the <i>in situ</i> generation of electrophilic sulfonamide salts. These electrophilic salts subsequently undergo nucleophilic substitution by alcohols, resulting in the formation of sulfonate esters under mild conditions. Other advantages of this method include the absence of transition-metal catalysts, broad substrate applicability, and high functional-group tolerance.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":" ","pages":"2268-2273"},"PeriodicalIF":4.9,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143514006","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}
We report a Pd-catalyzed decarboxylative Negishi coupling reaction for efficient biaryl synthesis from various zinc aryl carboxylates, including polyfluorobenzoates and heteroaryl carboxylates, using DMF as the solvent. This mild reaction exhibits a broad substrate scope and enables late-stage functionalization of bioactive molecules. Mechanistic studies show that DMF-assisted zinc catalyzes decarboxylation of polyfluorinated aryl carboxylates to generate arylzinc reagents in situ, which then undergo Negishi coupling catalyzed by palladium with arylthianthrenium salts to form biaryl compounds. Notably, this protocol represents a rare example of zinc-mediated decarboxylation and demonstrates a novel strategy for preparing arylzinc reagents from easily accessible (hetero)aryl carboxylic acids.
{"title":"Pd-Catalyzed Decarboxylative Negishi Coupling of Zinc Aryl Carboxylates with Arylthianthrenium Salts.","authors":"Chun Zhang, Yangbo Cui, Xiaoyu Zhou, Yichen Pan, Junqi Zhang, Dandan Hu, Hai-Ming Guo, Er-Jun Hao, Hongjun Ren","doi":"10.1021/acs.orglett.5c00408","DOIUrl":"10.1021/acs.orglett.5c00408","url":null,"abstract":"<p><p>We report a Pd-catalyzed decarboxylative Negishi coupling reaction for efficient biaryl synthesis from various zinc aryl carboxylates, including polyfluorobenzoates and heteroaryl carboxylates, using DMF as the solvent. This mild reaction exhibits a broad substrate scope and enables late-stage functionalization of bioactive molecules. Mechanistic studies show that DMF-assisted zinc catalyzes decarboxylation of polyfluorinated aryl carboxylates to generate arylzinc reagents in situ, which then undergo Negishi coupling catalyzed by palladium with arylthianthrenium salts to form biaryl compounds. Notably, this protocol represents a rare example of zinc-mediated decarboxylation and demonstrates a novel strategy for preparing arylzinc reagents from easily accessible (hetero)aryl carboxylic acids.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":" ","pages":"2256-2261"},"PeriodicalIF":4.9,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143514009","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}
We here report the use of a sterically tuned 2-fluoro-1-methylpyridinium salt for the catalyst-free, visible-light-mediated deoxygenative transformation of alcohols through alkoxypyridinium intermediates. The key to this process is the introduction of a bulky cyclohexyl group at the 3-position of the pyridinium ring, which enforces a favorable conformation for C–O bond cleavage and the formation of an electron donor–acceptor complex between the pyridinium ring and amines.
{"title":"A Sterically Tuned 2-Fluoropyridinium Salt for the Catalyst-Free, Visible-Light-Mediated Deoxygenation of Alcohols via an Electron Donor–Acceptor Complex","authors":"Takeshi Nanjo, Yixuan Lin, Yusei Fujii, Yoshiji Takemoto","doi":"10.1021/acs.orglett.5c00266","DOIUrl":"https://doi.org/10.1021/acs.orglett.5c00266","url":null,"abstract":"We here report the use of a sterically tuned 2-fluoro-1-methylpyridinium salt for the catalyst-free, visible-light-mediated deoxygenative transformation of alcohols through alkoxypyridinium intermediates. The key to this process is the introduction of a bulky cyclohexyl group at the 3-position of the pyridinium ring, which enforces a favorable conformation for C–O bond cleavage and the formation of an electron donor–acceptor complex between the pyridinium ring and amines.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"30 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143570325","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}
Pub Date : 2025-03-07DOI: 10.1021/acs.orglett.5c00641
Zeyuan Fu, Bingjie Rong, Liangbin Huang
Although aryl chlorides are among the most abundant and stable aromatic electrophiles, the coupling of aryl chlorides with isocyanides has remained an unsolved challenge. Herein, we report a general transformation of aryl chlorides, isocyanides, and thiocarboxylates to synthesize thioamides. The sterically hindered and electron-rich Josiphos ligand significantly facilitates the rate-determining oxidative addition step and reduces the toxicity of isocyanides toward the metal center. The combination of thiocarboxylate as the nucleophile and Josiphos as the ligands enabled the coupling-tolerated various 1°, 2°, and 3° isocyanides, which provides a rapid, efficient, and versatile method for the synthesis of large quantities of thioamides, including those of pharmaceutical relevance.
{"title":"Pd-Catalyzed Coupling of Aryl Chloride, Isocyanides, and Thiocarboxylate To Synthesize Thioamides","authors":"Zeyuan Fu, Bingjie Rong, Liangbin Huang","doi":"10.1021/acs.orglett.5c00641","DOIUrl":"https://doi.org/10.1021/acs.orglett.5c00641","url":null,"abstract":"Although aryl chlorides are among the most abundant and stable aromatic electrophiles, the coupling of aryl chlorides with isocyanides has remained an unsolved challenge. Herein, we report a general transformation of aryl chlorides, isocyanides, and thiocarboxylates to synthesize thioamides. The sterically hindered and electron-rich Josiphos ligand significantly facilitates the rate-determining oxidative addition step and reduces the toxicity of isocyanides toward the metal center. The combination of thiocarboxylate as the nucleophile and Josiphos as the ligands enabled the coupling-tolerated various 1°, 2°, and 3° isocyanides, which provides a rapid, efficient, and versatile method for the synthesis of large quantities of thioamides, including those of pharmaceutical relevance.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"2 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143570326","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}
Pub Date : 2025-03-07DOI: 10.1021/acs.orglett.5c00259
Tangfeng Yao, Chenchen Zhao, Chaokun Li, Qiuling Song
In comparison to alkyl monoboron or 1,2-diboron, which can generate alkyl radicals via tetracoordinate boron species under photocatalytic conditions, the participation of gem-diborons as substrates in such reactions remains to be developed. Herein, we report a method utilizing gem-diborons as starting materials to generate α-boryl radicals, which then react with various olefins, successfully and efficiently constructing a diverse range of high-value homoallylic boronates; meanwhile, the gem-difluorohomoallylic skeletons could also be smoothly obtained. This transformation demonstrates broad substrate scope and excellent tolerance toward functional groups, enhancing the utility of gem-diboron as precursors for C–C bond construction and the production of valuable products.
{"title":"Photoinduced Assembly of Diverse Homoallylic Boronates from gem-Diborons","authors":"Tangfeng Yao, Chenchen Zhao, Chaokun Li, Qiuling Song","doi":"10.1021/acs.orglett.5c00259","DOIUrl":"https://doi.org/10.1021/acs.orglett.5c00259","url":null,"abstract":"In comparison to alkyl monoboron or 1,2-diboron, which can generate alkyl radicals via tetracoordinate boron species under photocatalytic conditions, the participation of <i>gem</i>-diborons as substrates in such reactions remains to be developed. Herein, we report a method utilizing <i>gem</i>-diborons as starting materials to generate α-boryl radicals, which then react with various olefins, successfully and efficiently constructing a diverse range of high-value homoallylic boronates; meanwhile, the <i>gem</i>-difluorohomoallylic skeletons could also be smoothly obtained. This transformation demonstrates broad substrate scope and excellent tolerance toward functional groups, enhancing the utility of <i>gem</i>-diboron as precursors for C–C bond construction and the production of valuable products.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"53 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143570333","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}
Pub Date : 2025-03-07Epub Date: 2025-02-26DOI: 10.1021/acs.orglett.4c04629
John P Stasiak, K A Woerpel
Unsaturated hydroperoxides were synthesized from dienes using a regioselective cobalt-catalyzed hydroperoxidation reaction. Subsequent intramolecular oxa-Michael reactions in the presence of triethylammonium hydrochloride (HNEt3Cl) and catalytic Et3N formed 1,2-dioxanes, in several cases with high diastereoselectivity. These 1,2-dioxanes could be transformed to their respective carboxylic acids, without affecting the integrity of the peroxide linkage, to form compounds with structures that resemble biologically active natural products.
{"title":"Triethylamine-Catalyzed Cyclization of Unsaturated Hydroperoxides in the Presence of Triethylammonium Hydrochloride: A Synthesis of 1,2-Dioxanes.","authors":"John P Stasiak, K A Woerpel","doi":"10.1021/acs.orglett.4c04629","DOIUrl":"10.1021/acs.orglett.4c04629","url":null,"abstract":"<p><p>Unsaturated hydroperoxides were synthesized from dienes using a regioselective cobalt-catalyzed hydroperoxidation reaction. Subsequent intramolecular oxa-Michael reactions in the presence of triethylammonium hydrochloride (HNEt<sub>3</sub>Cl) and catalytic Et<sub>3</sub>N formed 1,2-dioxanes, in several cases with high diastereoselectivity. These 1,2-dioxanes could be transformed to their respective carboxylic acids, without affecting the integrity of the peroxide linkage, to form compounds with structures that resemble biologically active natural products.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":" ","pages":"2037-2041"},"PeriodicalIF":4.9,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143514027","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}
Pub Date : 2025-03-07Epub Date: 2025-02-26DOI: 10.1021/acs.orglett.5c00325
Jiyoon Song, Vikas R Aswar, Dnyandev B Jarhad, Lak Shin Jeong
Based on the promising biological activity of 6'-fluorocyclopentenyl-cytosine and -adenine, we report the design and synthesis of 6'-trifluoromethylcyclopentenyl-pyrimidine and -purine as potential antiviral agents. The introduction of a trifluoromethyl (CF3) group onto a sugar scaffold has been achieved using methyl fluorosulfonyldifluoroacetate (Chen's reagent) as a key step. The resulting trifluoromethylated sugar intermediate provides an efficient pathway for synthesizing various nucleoside analogues, facilitating the expansion of structure-activity relationship studies for neplanocin A analogues.
{"title":"Trifluoromethylation on a Nucleoside Sugar Scaffold: Design and Synthesis of 6'-Trifluoromethylcyclopentenyl-purine and -pyrimidine Nucleosides.","authors":"Jiyoon Song, Vikas R Aswar, Dnyandev B Jarhad, Lak Shin Jeong","doi":"10.1021/acs.orglett.5c00325","DOIUrl":"10.1021/acs.orglett.5c00325","url":null,"abstract":"<p><p>Based on the promising biological activity of 6'-fluorocyclopentenyl-cytosine and -adenine, we report the design and synthesis of 6'-trifluoromethylcyclopentenyl-pyrimidine and -purine as potential antiviral agents. The introduction of a trifluoromethyl (CF<sub>3</sub>) group onto a sugar scaffold has been achieved using methyl fluorosulfonyldifluoroacetate (Chen's reagent) as a key step. The resulting trifluoromethylated sugar intermediate provides an efficient pathway for synthesizing various nucleoside analogues, facilitating the expansion of structure-activity relationship studies for neplanocin A analogues.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":" ","pages":"2215-2219"},"PeriodicalIF":4.9,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143514029","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}
Coumarin skeletons are significant structural units frequently used in the fields of synthetic chemistry, medicinal chemistry, and materials science. Herein, we report a hemilabile P,N-ligand-assisted gold-catalyzed difunctionalization of activated alkynes with organohalides. The reaction occurs effectively under mild conditions without requiring an external oxidant, producing a variety of 3-arylated and alkenylated coumarin derivatives in high to excellent yields. This method demonstrates a wide substrate tolerance and superb functional group compatibility and is also suitable for heteroaromatic substrates. Further mechanistic investigations strongly support the proposed mechanism of the reaction.
{"title":"Gold-Catalyzed Difunctionalization of Activated Alkynes with Organohalides: Access to 3-Arylated and Alkenylated Coumarin Derivatives.","authors":"Yu Zhong, Yuanhao He, Yanfei Hu, Xingming Yan, Ruyi Zhang, Jumei Yi, Fen Zhao, Baomin Fan","doi":"10.1021/acs.orglett.5c00206","DOIUrl":"10.1021/acs.orglett.5c00206","url":null,"abstract":"<p><p>Coumarin skeletons are significant structural units frequently used in the fields of synthetic chemistry, medicinal chemistry, and materials science. Herein, we report a hemilabile P,N-ligand-assisted gold-catalyzed difunctionalization of activated alkynes with organohalides. The reaction occurs effectively under mild conditions without requiring an external oxidant, producing a variety of 3-arylated and alkenylated coumarin derivatives in high to excellent yields. This method demonstrates a wide substrate tolerance and superb functional group compatibility and is also suitable for heteroaromatic substrates. Further mechanistic investigations strongly support the proposed mechanism of the reaction.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":" ","pages":"2180-2185"},"PeriodicalIF":4.9,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143513996","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}
Pub Date : 2025-03-07DOI: 10.1021/acs.orglett.5c00692
Belén Martín-Matute, Nitin T. Patil, María Méndez, Xiaodong Shi
Published as part of <i>Organic Letters</i> virtual special issue “Gold-Mediated Chemistry”. The unique π-activation ability of gold has long served as the trademark for gold-catalyzed reactions. The reactivity of Au(I) and Au(III) complexes as excellent π-Lewis acids has been well explored by researchers, resulting in a plethora of publications in the past two decades. By leveraging the tunable π-activation properties, researchers continue to explore diverse reactivities such as the functionalization of C–C multiple bonds, enyne cycloisomerization, diyne cycloisomerization, carbene transfer reactions, etc. In recent years, the advances in Au(I)/Au(III) redox catalysis have gained momentum, making gold a potential contender in the realm of transition-metal-catalyzed cross-coupling reactions. In the context of enantioselective gold catalysis, recent years have witnessed the development of ligands for achieving enantioselective Au(I), Au(III), and Au(I)/Au(III) redox catalysis. In addition, merged gold/organocatalysis and gold-based bimetallic systems have emerged as intriguing strategies to achieve enantioselective transformations. The broad reactivity platform exhibited by gold complexes exemplifies their potential for significant applications in the total synthesis of highly functionalized compounds and even complex natural products. This Special Issue collects reports encompassing the diverse aspects of gold chemistry. <b>Xia</b> and colleagues report Suzuki–Miyaura cross-couplings of aryl iodides with aliphatic potassium trifluoroborates to form C(sp<sup>3</sup>)–C(sp<sup>2</sup>) bonds. The reaction operates through a Au(I)/Au(III) redox cycle facilitated by a hemilabile (P^N) ligand (DOI: 10.1021/acs.orglett.4c00755). A bifunctional ligand is also used in the gold-catalyzed homo- and heterodimerization of terminal alkynes, as demonstrated by <b>Wu and Zhang</b>. The ligand contains a weakly basic group, specifically a phosphine oxide, which facilitates alkyne deprotonation. This reaction occurs under mild conditions and exhibits excellent selectivity (DOI: 10.1021/acs.orglett.4c01872). <b>Echavarren</b> and co-workers showcase the versatility of Au(I) catalysis in the rapid synthesis of functionalized organic compounds. They present a three-component Au(I)-catalyzed alkoxyvinylation protocol involving acetylene, <i>N</i>-vinyl amides, and alcohols, yielding β-vinyl hemiaminals. Notably, when <i>N</i>,<i>N-</i>bisvinyl amines are reacted with acetylenes, the reaction leads to unique biscyclopropyl pyrrolidines (DOI: 10.1021/acs.orglett.4c02102). <b>Wang</b> and colleagues report the synthesis of a series of C–N and C–C axially chiral <i>N</i>-arylbenzo[<i>g</i>]indoles by exploiting a gold-catalyzed cascade cyclization of chiral diynes, leading to successful central-to-axial chirality transfer. The utility of this method was illustrated by transforming one of the products into a chiral phosphine, which successfully induced chirality in a Pd-c
{"title":"Gold-Mediated Chemistry Special Issue","authors":"Belén Martín-Matute, Nitin T. Patil, María Méndez, Xiaodong Shi","doi":"10.1021/acs.orglett.5c00692","DOIUrl":"https://doi.org/10.1021/acs.orglett.5c00692","url":null,"abstract":"Published as part of <i>Organic Letters</i> virtual special issue “Gold-Mediated Chemistry”. The unique π-activation ability of gold has long served as the trademark for gold-catalyzed reactions. The reactivity of Au(I) and Au(III) complexes as excellent π-Lewis acids has been well explored by researchers, resulting in a plethora of publications in the past two decades. By leveraging the tunable π-activation properties, researchers continue to explore diverse reactivities such as the functionalization of C–C multiple bonds, enyne cycloisomerization, diyne cycloisomerization, carbene transfer reactions, etc. In recent years, the advances in Au(I)/Au(III) redox catalysis have gained momentum, making gold a potential contender in the realm of transition-metal-catalyzed cross-coupling reactions. In the context of enantioselective gold catalysis, recent years have witnessed the development of ligands for achieving enantioselective Au(I), Au(III), and Au(I)/Au(III) redox catalysis. In addition, merged gold/organocatalysis and gold-based bimetallic systems have emerged as intriguing strategies to achieve enantioselective transformations. The broad reactivity platform exhibited by gold complexes exemplifies their potential for significant applications in the total synthesis of highly functionalized compounds and even complex natural products. This Special Issue collects reports encompassing the diverse aspects of gold chemistry. <b>Xia</b> and colleagues report Suzuki–Miyaura cross-couplings of aryl iodides with aliphatic potassium trifluoroborates to form C(sp<sup>3</sup>)–C(sp<sup>2</sup>) bonds. The reaction operates through a Au(I)/Au(III) redox cycle facilitated by a hemilabile (P^N) ligand (DOI: 10.1021/acs.orglett.4c00755). A bifunctional ligand is also used in the gold-catalyzed homo- and heterodimerization of terminal alkynes, as demonstrated by <b>Wu and Zhang</b>. The ligand contains a weakly basic group, specifically a phosphine oxide, which facilitates alkyne deprotonation. This reaction occurs under mild conditions and exhibits excellent selectivity (DOI: 10.1021/acs.orglett.4c01872). <b>Echavarren</b> and co-workers showcase the versatility of Au(I) catalysis in the rapid synthesis of functionalized organic compounds. They present a three-component Au(I)-catalyzed alkoxyvinylation protocol involving acetylene, <i>N</i>-vinyl amides, and alcohols, yielding β-vinyl hemiaminals. Notably, when <i>N</i>,<i>N-</i>bisvinyl amines are reacted with acetylenes, the reaction leads to unique biscyclopropyl pyrrolidines (DOI: 10.1021/acs.orglett.4c02102). <b>Wang</b> and colleagues report the synthesis of a series of C–N and C–C axially chiral <i>N</i>-arylbenzo[<i>g</i>]indoles by exploiting a gold-catalyzed cascade cyclization of chiral diynes, leading to successful central-to-axial chirality transfer. The utility of this method was illustrated by transforming one of the products into a chiral phosphine, which successfully induced chirality in a Pd-c","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"37 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143570322","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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