The direct ortho‐alkynylation of substituted phenylalanine has been successfully achieved through methoxyiminoacyl (MIA)‐mediated Pd‐catalyzed C−H functionalization. This innovative protocol showcases the ability to apply a diverse range of phenylalanine substrates, resulting in the efficient synthesis of alkynylation benzylamine derivatives with notable effectiveness. Computational investigations further revealed that the fluoride ion enhances the electropositivity of Pd(IV) and the interaction between C1 and C2 within the transition state of the reductive elimination, which significantly expedites the reductive elimination step in the alkynylation process.
{"title":"Experiment and Computational Study on Pd‐Catalyzed MIA‐Directed Ortho‐C−H Alkynlation of Phenylalanine","authors":"","doi":"10.1002/ajoc.202400159","DOIUrl":"10.1002/ajoc.202400159","url":null,"abstract":"<div><p>The direct <em>ortho</em>‐alkynylation of substituted phenylalanine has been successfully achieved through methoxyiminoacyl (MIA)‐mediated Pd‐catalyzed C−H functionalization. This innovative protocol showcases the ability to apply a diverse range of phenylalanine substrates, resulting in the efficient synthesis of alkynylation benzylamine derivatives with notable effectiveness. Computational investigations further revealed that the fluoride ion enhances the electropositivity of Pd(IV) and the interaction between C1 and C2 within the transition state of the reductive elimination, which significantly expedites the reductive elimination step in the alkynylation process.</p></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 7","pages":"Article e202400159"},"PeriodicalIF":2.8,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140931774","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The excellent reactivity of diaryliodonium salts has primarily been attributed to the efficient departure of the iodoarene unit, facilitating a variety of arylation reactions. However, one equivalent of iodoarene as a side‐product is a chemical waste in these reactions, which was criticized by chemists for hindering its popularity. Recently, the development of synthetic methodology that preserve the aryl iodine moiety received increasing attention. Oxidative rearrangement reactions involving aryliodonium reagents have significantly addressed the atom‐economic issue, thereby broadening the reaction scope. The resulting intricate aryliodine products are viewed as valuable synthons for the synthesis of natural products, pharmaceutical intermediates and other fine chemicals.
{"title":"Synthesis of Versatile Aryliodine Synthons by Aryliodonium Rearrangement Reactions","authors":"","doi":"10.1002/ajoc.202400129","DOIUrl":"10.1002/ajoc.202400129","url":null,"abstract":"<div><p>The excellent reactivity of diaryliodonium salts has primarily been attributed to the efficient departure of the iodoarene unit, facilitating a variety of arylation reactions. However, one equivalent of iodoarene as a side‐product is a chemical waste in these reactions, which was criticized by chemists for hindering its popularity. Recently, the development of synthetic methodology that preserve the aryl iodine moiety received increasing attention. Oxidative rearrangement reactions involving aryliodonium reagents have significantly addressed the atom‐economic issue, thereby broadening the reaction scope. The resulting intricate aryliodine products are viewed as valuable synthons for the synthesis of natural products, pharmaceutical intermediates and other fine chemicals.</p></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 7","pages":"Article e202400129"},"PeriodicalIF":2.8,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140932127","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
2‐Arylsulfonyl‐2‐azabicyclo[2.2.1]hept‐5‐enes, synthesized via the cycloaddition of chloral‐ or dichloro(phenyl)acetaldehyde N‐arylsulfonylimines to cyclopentadiene, undergo Wagner‐Meerwein rearrangement under the action of bromine or chlorine to afford 3‐polychloro‐6,7‐dyhalogenated 2‐arylsulfonylazabicyclo[2.2.1]heptanes.
{"title":"Polyhalogenated 2‐Azabicyclo[2.2.1]heptanes from Polyhaloaldimines and Cyclopentadiene via Cycloaddition and Wagner‐Meerwein Rearrangement","authors":"","doi":"10.1002/ajoc.202400017","DOIUrl":"10.1002/ajoc.202400017","url":null,"abstract":"<div><p>2‐Arylsulfonyl‐2‐azabicyclo[<em>2.2.1</em>]hept‐5‐enes, synthesized via the cycloaddition of chloral‐ or dichloro(phenyl)acetaldehyde <em>N</em>‐arylsulfonylimines to cyclopentadiene, undergo Wagner‐Meerwein rearrangement under the action of bromine or chlorine to afford 3‐polychloro‐6,7‐dyhalogenated 2‐arylsulfonylazabicyclo[<em>2.2.1</em>]heptanes.</p></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 7","pages":"Article e202400017"},"PeriodicalIF":2.8,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140204534","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A convenient route for the preparation of tetrahydropyran (THP) derivatives with a quaternary and tertiary vicinal stereocenters is reported. The atom economy acid‐catalyzed cyclization of allylsilyl alcohols provided polysubstituted tetrahydropyrans in good yields and excellent diastereoselectivities (>95 : 5). In comparison with the traditional oxymercuration procedure, this approach resulted to be more efficient in both yield and stereocontrol.
{"title":"Stereoselective Synthesis of Polysubstituted Tetrahydropyrans by Brønsted Acid‐Mediated Hydroxyalkoxylation of Silylated Alkenols","authors":"","doi":"10.1002/ajoc.202400096","DOIUrl":"10.1002/ajoc.202400096","url":null,"abstract":"<div><p>A convenient route for the preparation of tetrahydropyran (THP) derivatives with a quaternary and tertiary vicinal stereocenters is reported. The atom economy acid‐catalyzed cyclization of allylsilyl alcohols provided polysubstituted tetrahydropyrans in good yields and excellent diastereoselectivities (>95 : 5). In comparison with the traditional oxymercuration procedure, this approach resulted to be more efficient in both yield and stereocontrol.</p></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 7","pages":"Article e202400096"},"PeriodicalIF":2.8,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ajoc.202400096","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140579951","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Palladium‐catalyzed carbonylation of aryl sulfonium salts with CO2 as a CO surrogate has been successfully developed via a one‐pot two‐step procedure. Thus, by merging thianthrenation and the carbonylation, site‐selective aromatic C−H carbonylation of a plethora of readily available arenes can be realized with CO2, providing access to a variety of structurally diverse and useful benzamides, esters and carboxylic acids. Simple operation, broad substrate scope, good functional group tolerance and mild reaction conditions are the attractive features of the method. Late‐stage functionalization of complex bioactive molecules as well as the precise synthesis of pharmaceuticals 1‐BCP and butoxycaine demonstrated the potential application of the established protocol.
钯催化的芳基锍盐羰基化反应以二氧化碳作为一氧化碳代用品,通过一步法两步法已成功开发出来。因此,通过合并噻蒽化合和羰基化反应,可以用 CO2 对大量易得的炔烃进行位点选择性芳香 C-H 羰基化反应,从而获得各种结构多样且有用的苯甲酰胺、酯和羧酸。该方法具有操作简单、底物范围广、官能团耐受性好和反应条件温和等诱人特点。复杂生物活性分子的后期功能化以及药物 1-BCP 和丁氧基卡因的精确合成,都证明了这一既定方案的潜在应用价值。
{"title":"Palladium‐Catalyzed Carbonylation of Aryl Sulfonium Salts with CO2 as a CO Surrogate","authors":"","doi":"10.1002/ajoc.202400142","DOIUrl":"10.1002/ajoc.202400142","url":null,"abstract":"<div><p>Palladium‐catalyzed carbonylation of aryl sulfonium salts with CO<sub>2</sub> as a CO surrogate has been successfully developed via a one‐pot two‐step procedure. Thus, by merging thianthrenation and the carbonylation, site‐selective aromatic C−H carbonylation of a plethora of readily available arenes can be realized with CO<sub>2</sub>, providing access to a variety of structurally diverse and useful benzamides, esters and carboxylic acids. Simple operation, broad substrate scope, good functional group tolerance and mild reaction conditions are the attractive features of the method. Late‐stage functionalization of complex bioactive molecules as well as the precise synthesis of pharmaceuticals 1‐BCP and butoxycaine demonstrated the potential application of the established protocol.</p></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 7","pages":"Article e202400142"},"PeriodicalIF":2.8,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140580101","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A procedure utilizing [TBA][P(SiCl3)2] as P source for the synthesis of phosphinecarboxamides is presented. The synthesis involves the reaction of [TBA][P(SiCl3)2] with isocyanates. These compounds act as highly effective reagents for the subsequent phosphination of isocyanates, leading to the formation of phosphine(triscarboxamides). This reaction proceeds swiftly under mild and straightforward conditions, making it suitable for a wide range of commercially available isocyanates.
本文介绍了利用 [TBA][P(SiCl3)2]作为 P 源合成膦甲酰胺的过程。合成过程包括 [TBA][P(SiCl3)2]与异氰酸酯的反应。这些化合物是异氰酸酯随后磷化的高效试剂,可生成膦(三碳酰胺)。该反应在温和直接的条件下迅速进行,因此适用于多种市售异氰酸酯。
{"title":"Mild and Catalyst‐Free Phosphination of Isocyanates with [TBA][P(SiCl3)2] for the Synthesis of Phosphinecarboxamides","authors":"","doi":"10.1002/ajoc.202400178","DOIUrl":"10.1002/ajoc.202400178","url":null,"abstract":"<div><p>A procedure utilizing [TBA][P(SiCl<sub>3</sub>)<sub>2</sub>] as P source for the synthesis of phosphinecarboxamides is presented. The synthesis involves the reaction of [TBA][P(SiCl<sub>3</sub>)<sub>2</sub>] with isocyanates. These compounds act as highly effective reagents for the subsequent phosphination of isocyanates, leading to the formation of phosphine(triscarboxamides). This reaction proceeds swiftly under mild and straightforward conditions, making it suitable for a wide range of commercially available isocyanates.</p></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 7","pages":"Article e202400178"},"PeriodicalIF":2.8,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140839443","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A general and convenient selective direct arylation of the 3‐position of triimidazo[1,2‐a:1’,2’‐c:1’’,2’’‐e][1,3,5]triazine (1) with (hetero)aryl halides in DMA was successfully achieved in the presence of K2CO3 as the base and a catalyst precursor consisting of Pd(OAc)2 and P(2‐furyl)3. Electron‐poor and ‐rich (hetero)aryl moieties, including the strongly deactivated and sterically encumbered 2,4,6‐trimethoxyphenyl unit, are well tolerated in the electrophilic partner. The data obtained in this synthetic study support a reaction mechanism involving an electrophilic attack of an arylpalladium‐(II) halide species onto the triazine ring.
{"title":"Synthesis of 3‐Aryl Substituted Triimidazotriazines via Regioselective Direct Arylation","authors":"","doi":"10.1002/ajoc.202400082","DOIUrl":"10.1002/ajoc.202400082","url":null,"abstract":"<div><p>A general and convenient selective direct arylation of the 3‐position of triimidazo[1,2‐a:1’,2’‐c:1’’,2’’‐e][1,3,5]triazine (<strong>1</strong>) with (hetero)aryl halides in DMA was successfully achieved in the presence of K<sub>2</sub>CO<sub>3</sub> as the base and a catalyst precursor consisting of Pd(OAc)<sub>2</sub> and P(2‐furyl)<sub>3</sub>. Electron‐poor and ‐rich (hetero)aryl moieties, including the strongly deactivated and sterically encumbered 2,4,6‐trimethoxyphenyl unit, are well tolerated in the electrophilic partner. The data obtained in this synthetic study support a reaction mechanism involving an electrophilic attack of an arylpalladium‐(II) halide species onto the triazine ring.</p></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 7","pages":"Article e202400082"},"PeriodicalIF":2.8,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140602580","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Attempts to carry out intramolecular annulation of 9,10‐diarylbenzo[h]quinolines and 9,10‐di(hetero)arylphenanthrenes to aromatics with expanded π‐conjugated systems by using different methods are described. The starting compounds (9,10‐diarylbenzo[h]quinolines and 9,10‐di(hetero)arylphenanthrenes) were prepared by C−C bond activation in 1‐azabiphenylene or biphenylene followed by insertion of internal alkynes. Interestingly, unlike in purely carbon‐based aromatics, the course of the annulation turned out to be highly dependent on the structure of maternal compounds. In a handful of cases were obtained the expected or desired products. In others, unexpected rearrangements of the basic molecular frameworks were observed.
{"title":"Biphenylene and 1‐Azabiphenylene as a Platform for Synthesis of Azapolyaromatic Compounds","authors":"","doi":"10.1002/ajoc.202400126","DOIUrl":"10.1002/ajoc.202400126","url":null,"abstract":"<div><p>Attempts to carry out intramolecular annulation of 9,10‐diarylbenzo[<em>h</em>]quinolines and 9,10‐di(hetero)arylphenanthrenes to aromatics with expanded π‐conjugated systems by using different methods are described. The starting compounds (9,10‐diarylbenzo[<em>h</em>]quinolines and 9,10‐di(hetero)arylphenanthrenes) were prepared by C−C bond activation in 1‐azabiphenylene or biphenylene followed by insertion of internal alkynes. Interestingly, unlike in purely carbon‐based aromatics, the course of the annulation turned out to be highly dependent on the structure of maternal compounds. In a handful of cases were obtained the expected or desired products. In others, unexpected rearrangements of the basic molecular frameworks were observed.</p></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 7","pages":"Article e202400126"},"PeriodicalIF":2.8,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ajoc.202400126","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140625583","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The total syntheses of eutyscoparol A and violaceoid C via violaceoid A, have been accomplished including the improved total syntheses of violaceoid A and violaceoid B. This synthetic method, which employed the desymmetrization of a symmetric diol, enabled divergent access to other violaceoids, eutyscoparols, and their derivatives.
我们完成了丁香油酚 A 的全合成和通过类中提琴酸 A 合成类中提琴酸 C 的全合成,包括改进了类中提琴酸 A 和类中提琴酸 B 的全合成。这种合成方法采用了不对称二元醇的非对称化技术,从而能够以不同的方法获得其他类长春花碱、丁香油醇及其衍生物。
{"title":"Total Synthesis of Eutyscoparol A and Violaceoid C","authors":"","doi":"10.1002/ajoc.202400148","DOIUrl":"10.1002/ajoc.202400148","url":null,"abstract":"<div><p>The total syntheses of eutyscoparol A and violaceoid C <em>via</em> violaceoid A, have been accomplished including the improved total syntheses of violaceoid A and violaceoid B. This synthetic method, which employed the desymmetrization of a symmetric diol, enabled divergent access to other violaceoids, eutyscoparols, and their derivatives.</p></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 7","pages":"Article e202400148"},"PeriodicalIF":2.8,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ajoc.202400148","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140656488","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The development of a low‐cost, reusable, and sustainable approach is a difficult and emerging demand in the coming arena. Here, we demonstrate the selective oxidation of primary alcohol, styrene to aldehyde, and alkyl benzene to appropriate ketone, under Blue LED irradiation. The developed approaches employ reusable catalysts (V2O5/TIO2) and green solvents (ACN, H2O) at room temperature. The substrate scope is widely investigated for various compounds of different functionalities. Organic transformations are supported by reaction mechanistic studies. The gram scale reaction and catalytic recyclability were also carried out to maximize the protocol's synthetic utility.
开发一种低成本、可重复使用和可持续的方法是一个难题,也是未来新出现的需求。在此,我们展示了在蓝光 LED 的照射下将伯醇、苯乙烯氧化成醛以及将烷基苯氧化成适当酮的选择性氧化方法。所开发的方法采用了可重复使用的催化剂(V2O5/TIO2)和室温下的绿色溶剂(ACN、H2O)。针对不同官能团的各种化合物,对底物范围进行了广泛研究。反应机理研究为有机转化提供了支持。此外,还进行了克级反应和催化剂可回收性研究,以最大限度地提高该方案的合成效用。
{"title":"Photocatalytic (V2O5/TiO2) Blue LED Mediated Selective Oxidation of Alcohols, Styrene to Aldehydes, and Oxygenation of Alkyl‐Benzene to Ketones","authors":"","doi":"10.1002/ajoc.202400088","DOIUrl":"10.1002/ajoc.202400088","url":null,"abstract":"<div><p>The development of a low‐cost, reusable, and sustainable approach is a difficult and emerging demand in the coming arena. Here, we demonstrate the selective oxidation of primary alcohol, styrene to aldehyde, and alkyl benzene to appropriate ketone, under Blue LED irradiation. The developed approaches employ reusable catalysts (V<sub>2</sub>O<sub>5</sub>/TIO<sub>2</sub>) and green solvents (ACN, H<sub>2</sub>O) at room temperature. The substrate scope is widely investigated for various compounds of different functionalities. Organic transformations are supported by reaction mechanistic studies. The gram scale reaction and catalytic recyclability were also carried out to maximize the protocol's synthetic utility.</p></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 7","pages":"Article e202400088"},"PeriodicalIF":2.8,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140580210","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}