Ligands play a key role in asymmetric transition-metal catalysis. Among reported chiral ligands, readily available and air-stable secondary phosphine oxide ligands are unique and have aroused wide interest in Ni–Al bimetallic catalysis, since they can act as bifunctional ligands to ligate two metals for stronger bimetallic synergism, greatly enhancing reactivity and selectivity. Hence, in this mini review we will focus on secondary phosphine oxides and their applications in asymmetric Ni-Al bimetallic catalysis.
{"title":"Chiral Secondary Phosphine Oxide Ligands in Asymmetric Ni–Al Bimetallic Catalysis","authors":"Mengying Xu, Weiwei Xu, Mengchun Ye","doi":"10.1002/ejoc.202401000","DOIUrl":"https://doi.org/10.1002/ejoc.202401000","url":null,"abstract":"Ligands play a key role in asymmetric transition-metal catalysis. Among reported chiral ligands, readily available and air-stable secondary phosphine oxide ligands are unique and have aroused wide interest in Ni–Al bimetallic catalysis, since they can act as bifunctional ligands to ligate two metals for stronger bimetallic synergism, greatly enhancing reactivity and selectivity. Hence, in this mini review we will focus on secondary phosphine oxides and their applications in asymmetric Ni-Al bimetallic catalysis.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142563220","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jan Radolko, Ha N Do, Peter Ehlers, Alexander Villinger, Peter Langer
6‑Oxazaaceanthrylenes have been synthesized for the first time via a selective SNAr reaction or Ullmann-coupling of phenols, followed by a C-H activation reaction. The reaction has been carefully optimized and permits the selective synthesis of N,O-doped aceanthrylenes in moderate to excellent yields and tolerate various functional groups. The aromatic behavior of the hitherto unknown heterocyclic scaffold has been further analyzed by NICS and NICS2BC calculations.
{"title":"Synthesis and Properties of 6-Oxazaaceanthrylenes","authors":"Jan Radolko, Ha N Do, Peter Ehlers, Alexander Villinger, Peter Langer","doi":"10.1002/ejoc.202401045","DOIUrl":"https://doi.org/10.1002/ejoc.202401045","url":null,"abstract":"6‑Oxazaaceanthrylenes have been synthesized for the first time via a selective SNAr reaction or Ullmann-coupling of phenols, followed by a C-H activation reaction. The reaction has been carefully optimized and permits the selective synthesis of N,O-doped aceanthrylenes in moderate to excellent yields and tolerate various functional groups. The aromatic behavior of the hitherto unknown heterocyclic scaffold has been further analyzed by NICS and NICS2BC calculations.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142562174","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
We investigated a convergent synthesis of aplysiatoxin analogs based on a combination of ring-closing and cross metathesis. The route provided four analogs (3a–d) with different side chains to determine the CH/π interaction with protein kinase C (PKC)-C1 domains. Biochemical evaluation revealed that a naphthol moiety did not improve binding to PKC-C1 domains, suggesting that the hydrogen bonding of the hydroxy group with the PKC-C1 domains may be more important than the CH/π interaction.
{"title":"Convergent Synthesis of Antitumor Aplysiatoxin Derivatives Based on a Combination of Ring-closing and Cross Metathesis","authors":"Mako Aoki, Hiroto Takarada, Jumpei Maki, Takumi Kobayashi, Chihiro Tsukano, Kazuhiro Irie","doi":"10.1002/ejoc.202401074","DOIUrl":"https://doi.org/10.1002/ejoc.202401074","url":null,"abstract":"We investigated a convergent synthesis of aplysiatoxin analogs based on a combination of ring-closing and cross metathesis. The route provided four analogs (3a–d) with different side chains to determine the CH/π interaction with protein kinase C (PKC)-C1 domains. Biochemical evaluation revealed that a naphthol moiety did not improve binding to PKC-C1 domains, suggesting that the hydrogen bonding of the hydroxy group with the PKC-C1 domains may be more important than the CH/π interaction.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142562204","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Recent advances in the continuous synthesis of ionic liquids and SILP-assisted continuous processes are reviewed in this manuscript. These catalyst frameworks still provide an attractive strategy in many organic transformations and provide a suitable tool for designing new synthetic approaches. This review focuses on recent developments in the research area from 2016 up until today.
{"title":"Flowing Forward: Continuous Synthesis of and with Ionic Liquids","authors":"Kristof Stagel, Katharina Bica-Schröder","doi":"10.1002/ejoc.202400917","DOIUrl":"https://doi.org/10.1002/ejoc.202400917","url":null,"abstract":"Recent advances in the continuous synthesis of ionic liquids and SILP-assisted continuous processes are reviewed in this manuscript. These catalyst frameworks still provide an attractive strategy in many organic transformations and provide a suitable tool for designing new synthetic approaches. This review focuses on recent developments in the research area from 2016 up until today.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142563322","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tianbo Shang, Chao Ma, Mengyu Xie, Tao Cai, Yuzhen Gao
Benzo[b]thiophene moieties are important skeletons which have been widely found in many natural products, pharmaceuticals, as well as functionalized materials. 2-Alkynylthioanisoles, a class of bifunctional compounds bearing methylthio and alkynyl groups, are easily accessible from Pd-catalyzed Sonogashira coupling between 2-halothioanisoles and terminal alkynes, which have been widely employed as synthons in the construction of benzo[b]thiophenes through an electrophilic or a radical pathway. This review summarizes the related developments with a particular focus on the reaction mechanism. We hope it will help in future research in this area and believe that with the discovery of new catalytic systems, the industrial synthesis of benzo[b]thiophenes from 2-alkynylthioanisoles will be achieved soon.
{"title":"Developments in the Construction of Benzo[b]thiophenes from 2-Alkynylthioanisoles by Electrophilic and Radical Cyclization Reactions","authors":"Tianbo Shang, Chao Ma, Mengyu Xie, Tao Cai, Yuzhen Gao","doi":"10.1002/ejoc.202401059","DOIUrl":"https://doi.org/10.1002/ejoc.202401059","url":null,"abstract":"Benzo[b]thiophene moieties are important skeletons which have been widely found in many natural products, pharmaceuticals, as well as functionalized materials. 2-Alkynylthioanisoles, a class of bifunctional compounds bearing methylthio and alkynyl groups, are easily accessible from Pd-catalyzed Sonogashira coupling between 2-halothioanisoles and terminal alkynes, which have been widely employed as synthons in the construction of benzo[b]thiophenes through an electrophilic or a radical pathway. This review summarizes the related developments with a particular focus on the reaction mechanism. We hope it will help in future research in this area and believe that with the discovery of new catalytic systems, the industrial synthesis of benzo[b]thiophenes from 2-alkynylthioanisoles will be achieved soon.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142562173","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The synthesis of axially chiral carbonyl compounds has attracted considerable interest in organic synthesis due to their prevalence in natural products and pharmaceuticals, as well as their utility in material science and catalysis. Transition‐metal‐catalyzed approaches have become powerful tools for their construction, offering high efficiency, selectivity, and versatility among the various methods developed. This concept aims to provide a comprehensive overview of recent advances in the transition‐metal‐catalyzed asymmetric synthesis of axially chiral carbonyl compounds, integrating scattered work with different catalytic systems. This feature concept is divided into four types of reactions based on the strategies employed: cross‐coupling reactions, cycloaddition reactions, desymmetrization reactions, and other C‒H activation reactions.
{"title":"Transition‐Metal‐Catalyzed Construction of Axially Chiral Carbonyl Compounds","authors":"Yu Yan, Min Pan, Jialin Ming, Jun-Ping Yue, Xiao-Wang Chen, Yong-Yuan Gui, Da-Gang Yu","doi":"10.1002/ejoc.202400995","DOIUrl":"https://doi.org/10.1002/ejoc.202400995","url":null,"abstract":"The synthesis of axially chiral carbonyl compounds has attracted considerable interest in organic synthesis due to their prevalence in natural products and pharmaceuticals, as well as their utility in material science and catalysis. Transition‐metal‐catalyzed approaches have become powerful tools for their construction, offering high efficiency, selectivity, and versatility among the various methods developed. This concept aims to provide a comprehensive overview of recent advances in the transition‐metal‐catalyzed asymmetric synthesis of axially chiral carbonyl compounds, integrating scattered work with different catalytic systems. This feature concept is divided into four types of reactions based on the strategies employed: cross‐coupling reactions, cycloaddition reactions, desymmetrization reactions, and other C‒H activation reactions.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142561908","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
We report a catalytic late-stage bromination strategy for the α-C-H functionalization of aryl acetic acid. The aryl acetic acid was transformed into enediolate in the presence of an (AcO)4B2O with the combination of DBU, and consequently underwent an electrophilic bromination reaction with pyridinium tribromide. A wide range of α-bromo aryl acetic acids were isolated in yields of 19-65%. In addition, the reaction could be performed on a gram scale, and several transformations of the products were carried out.
{"title":"The Catalytic Synthesis of α-Bromo Aryl Acetic Acids by Late-Stage Bromination","authors":"Junyu Wang, Xin Wu, Beining Wang, Xiangyang Yuan, Shengnan Yang, Haipeng Hu","doi":"10.1002/ejoc.202400962","DOIUrl":"https://doi.org/10.1002/ejoc.202400962","url":null,"abstract":"We report a catalytic late-stage bromination strategy for the α-C-H functionalization of aryl acetic acid. The aryl acetic acid was transformed into enediolate in the presence of an (AcO)4B2O with the combination of DBU, and consequently underwent an electrophilic bromination reaction with pyridinium tribromide. A wide range of α-bromo aryl acetic acids were isolated in yields of 19-65%. In addition, the reaction could be performed on a gram scale, and several transformations of the products were carried out.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142562175","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Alkenes and alkynes are inexpensive and readily available basic chemicals. Silyl radical-participated silylation of alkenes and alkynes provides a powerful tool for the direct construction of organosilicon compounds. Compared to hydrosilylation reactions, silylfunctionalization reactions are more attractive and advantageous in building diverse organosilicon compounds, which has led to their becoming a research focus in organic synthesis. Herein, we provide a comprehensive overview of recent advances in silyl radical-participated silylfunctionalization of alkenes and alkynes.
{"title":"Silyl Radical-Participated Silylfunctionalization of Alkenes and Alkynes","authors":"Yang Zheng, Yi-Jie Zhu, Yi-Nan Zhang, Fei Chen","doi":"10.1002/ejoc.202401018","DOIUrl":"https://doi.org/10.1002/ejoc.202401018","url":null,"abstract":"Alkenes and alkynes are inexpensive and readily available basic chemicals. Silyl radical-participated silylation of alkenes and alkynes provides a powerful tool for the direct construction of organosilicon compounds. Compared to hydrosilylation reactions, silylfunctionalization reactions are more attractive and advantageous in building diverse organosilicon compounds, which has led to their becoming a research focus in organic synthesis. Herein, we provide a comprehensive overview of recent advances in silyl radical-participated silylfunctionalization of alkenes and alkynes.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142562134","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
An atroposelective synthesis of axially chiral N‐arylindolines has been established by organocatalytic nucleophilic amination of arenes with 7‐substituted indolines, providing a straightforward way to achieve the expected C‐N atropisomers in good yields (up to 95%) with good to excellent enantioselectivities (up to 97% ee) from readily available starting materials. Furthermore, axially chiral N‐arylindole derivatives could be prepared upon oxidative aromatization of the corresponding N‐arylindolines.
{"title":"Organocatalytic Atroposelective C‐H Amination of Arenes with Indolines","authors":"Jiangtao Sun, Tiantian Wang, Shaoran An","doi":"10.1002/ejoc.202401070","DOIUrl":"https://doi.org/10.1002/ejoc.202401070","url":null,"abstract":"An atroposelective synthesis of axially chiral N‐arylindolines has been established by organocatalytic nucleophilic amination of arenes with 7‐substituted indolines, providing a straightforward way to achieve the expected C‐N atropisomers in good yields (up to 95%) with good to excellent enantioselectivities (up to 97% ee) from readily available starting materials. Furthermore, axially chiral N‐arylindole derivatives could be prepared upon oxidative aromatization of the corresponding N‐arylindolines.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142561909","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Meng-Ze Jia, Bin Tan, Yun-Rui Chen, Jia-Qi Pan, Shi-Kai Yu, Ling Xin, Jie Zhang
Through effective regulation of active species in photocatalytic process, the oxidation or C(sp3)-S bond cleavage upgrading of widespread aryl alkyl sulfides under mild conditions was successfully achieved by using a pyridinium photocatalyst. Benefiting from the excellent redox ability of the photocatalyst, the electron transfer between the pyridinium molecule and the substrate, molecular oxygen, or counter-anion effectively promotes the conversion and upgrading of the substrate thioether. Among them, the efficient generation of reactive oxygen species (ROS) enables the highly selective oxidation of sulfides to sulfoxides under visible light and air atmosphere. More importantly, the chlorine radical (Cl•) generated by electron transfer, reported for the first time, contributes to the cleavage of C(sp3)-S bonds, achieving the transformation of aryl alkyl sulfides to disulfides. By harnessing the superior photocatalytic ability of pyridinium molecules, this work not only achieves the highly selective conversion of thioether by taming the active species in the photocatalytic process, but also sheds light on the untapped potential of chlorine radicals in the field of C(sp3)-S bond activation and cleavage.
{"title":"Tunable and selective transformation of aromatic thioether enabled by regulating active species under visible light irradiation","authors":"Meng-Ze Jia, Bin Tan, Yun-Rui Chen, Jia-Qi Pan, Shi-Kai Yu, Ling Xin, Jie Zhang","doi":"10.1002/ejoc.202401092","DOIUrl":"https://doi.org/10.1002/ejoc.202401092","url":null,"abstract":"Through effective regulation of active species in photocatalytic process, the oxidation or C(sp3)-S bond cleavage upgrading of widespread aryl alkyl sulfides under mild conditions was successfully achieved by using a pyridinium photocatalyst. Benefiting from the excellent redox ability of the photocatalyst, the electron transfer between the pyridinium molecule and the substrate, molecular oxygen, or counter-anion effectively promotes the conversion and upgrading of the substrate thioether. Among them, the efficient generation of reactive oxygen species (ROS) enables the highly selective oxidation of sulfides to sulfoxides under visible light and air atmosphere. More importantly, the chlorine radical (Cl•) generated by electron transfer, reported for the first time, contributes to the cleavage of C(sp3)-S bonds, achieving the transformation of aryl alkyl sulfides to disulfides. By harnessing the superior photocatalytic ability of pyridinium molecules, this work not only achieves the highly selective conversion of thioether by taming the active species in the photocatalytic process, but also sheds light on the untapped potential of chlorine radicals in the field of C(sp3)-S bond activation and cleavage.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142541981","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：