Wenxue Li , Junwu Li , Fengkai Sun , Man Miao , Xiao‐Bing Lan , Jian‐Qiang Yu , Pengpeng Liu , Houyuan Li , Rui Wang , Jian Zhang , Zhenyu An
A direct electrochemical redox reaction of olefins and disulfides/thiols/diselenides without external oxidants has been developed, which includes the hydroxychalcogenation of olefins. This procedure exhibited good functional group tolerance, and a series of β‐hydroxysulfide/β‐hydroxyselenide derivatives were obtained in moderate to good yields. Mechanistic studies and cyclic voltammetry were also conducted to elucidate the reaction process.
{"title":"Electrochemical Oxidative Hydroxychalcogenation of Olefins with Disulfides/Thiols/Diselenides and H2O as Nucleophilic Oxygen Sources","authors":"Wenxue Li , Junwu Li , Fengkai Sun , Man Miao , Xiao‐Bing Lan , Jian‐Qiang Yu , Pengpeng Liu , Houyuan Li , Rui Wang , Jian Zhang , Zhenyu An","doi":"10.1002/ejoc.202401226","DOIUrl":"10.1002/ejoc.202401226","url":null,"abstract":"<div><div>A direct electrochemical redox reaction of olefins and disulfides/thiols/diselenides without external oxidants has been developed, which includes the hydroxychalcogenation of olefins. This procedure exhibited good functional group tolerance, and a series of <em>β</em>‐hydroxysulfide/<em>β</em>‐hydroxyselenide derivatives were obtained in moderate to good yields. Mechanistic studies and cyclic voltammetry were also conducted to elucidate the reaction process.</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"28 7","pages":"Article e202401226"},"PeriodicalIF":2.5,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142805137","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}
Full‐color fluorescence solvatochromism was demonstrated using two carbon‐bridged oligo(phenylenevinylene) (COPV) derivatives Ph2N‐COPV1(Bu)‐COCH3 and [Ph2N‐COPV1(Bu)]2CO with a push–pull system, where the donor and acceptor moieties are diphenylamino and a carbonyl group, respectively. In non‐polar cyclohexane, the molecules exhibited blue photoluminescence (λPL = 443 and 464 nm) with a locally excited character, while in polar solvents, a charge‐transfer character emerged. In methanol, red emission was observed (λPL = 602 and 572 nm). The difference in luminescence maxima between cyclohexane and methanol corresponds to 0.74 and 0.59 eV for Ph2N‐COPV1(Bu)‐COCH3 and [Ph2N‐COPV1(Bu)]2CO, respectively, which are larger than those of previously reported push–pull systems. The photoluminescence quantum yields of Ph2N‐COPV1(Bu)‐COCH3 in aprotic solvents were 0.90 and higher regardless of solvent polarity, while they decreased in protic solvents. The molecules also display high extinction coefficients of up to 2.8 x 104 and 6.4 x 104 M⁻¹cm⁻¹. These data demonstrate the effectiveness of the use of structurally rigid planar COPV framework. Furthermore, [Ph2N‐COPV1(Bu)]2CO showed significant responses to water content in tetrahydrofuran‐water mixed solvents, which highlights its potential for sensing applications.
{"title":"Full‐color Fluorescence Solvatochromism of Push‐pull Type Indenoindene Derivatives","authors":"Wakana Kanezaki, Ryutaro Ishikawa, Hayato Tsuji","doi":"10.1002/ejoc.202401471","DOIUrl":"https://doi.org/10.1002/ejoc.202401471","url":null,"abstract":"Full‐color fluorescence solvatochromism was demonstrated using two carbon‐bridged oligo(phenylenevinylene) (COPV) derivatives Ph2N‐COPV1(Bu)‐COCH3 and [Ph2N‐COPV1(Bu)]2CO with a push–pull system, where the donor and acceptor moieties are diphenylamino and a carbonyl group, respectively. In non‐polar cyclohexane, the molecules exhibited blue photoluminescence (λPL = 443 and 464 nm) with a locally excited character, while in polar solvents, a charge‐transfer character emerged. In methanol, red emission was observed (λPL = 602 and 572 nm). The difference in luminescence maxima between cyclohexane and methanol corresponds to 0.74 and 0.59 eV for Ph2N‐COPV1(Bu)‐COCH3 and [Ph2N‐COPV1(Bu)]2CO, respectively, which are larger than those of previously reported push–pull systems. The photoluminescence quantum yields of Ph2N‐COPV1(Bu)‐COCH3 in aprotic solvents were 0.90 and higher regardless of solvent polarity, while they decreased in protic solvents. The molecules also display high extinction coefficients of up to 2.8 x 104 and 6.4 x 104 M⁻¹cm⁻¹. These data demonstrate the effectiveness of the use of structurally rigid planar COPV framework. Furthermore, [Ph2N‐COPV1(Bu)]2CO showed significant responses to water content in tetrahydrofuran‐water mixed solvents, which highlights its potential for sensing applications.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"16 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418430","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}
Quinolino[4,3‐j]phenanthridines were synthesized from para‐terphenyl‐2,2′′‐diamines, which were obtained by cross‐coupling reactions. The diamines were converted into amides and ortho‐cyclized to quinolino[4,3‐j]phenanthridines using Morgan‐Walls reactions. Prolonged reaction times were required in these electrophilic substitution reactions to overcome the respective deactivated intermediates formed after the first ortho fusion. Optophysical properties were determined by UV/Vis and fluorescence spectroscopy and calculated by quantum chemical calculations. The compounds exhibit rather small HOMO/LUMO gaps and a remarkable bathochromic shift of luminescence upon protonation, what makes these compounds promising candidates for optoelectronic applications.
{"title":"Synthesis of Quinolino[4,3‐j]phenanthridines and their Photophysical Characterization","authors":"Felix R. Schumann, Joachim Podlech","doi":"10.1002/ejoc.202401416","DOIUrl":"https://doi.org/10.1002/ejoc.202401416","url":null,"abstract":"Quinolino[4,3‐<jats:italic>j</jats:italic>]phenanthridines were synthesized from <jats:italic>para</jats:italic>‐terphenyl‐2,2′′‐diamines, which were obtained by cross‐coupling reactions. The diamines were converted into amides and <jats:italic>ortho</jats:italic>‐cyclized to quinolino[4,3‐<jats:italic>j</jats:italic>]phenanthridines using <jats:italic>Morgan‐Walls</jats:italic> reactions. Prolonged reaction times were required in these electrophilic substitution reactions to overcome the respective deactivated intermediates formed after the first <jats:italic>ortho</jats:italic> fusion. Optophysical properties were determined by UV/Vis and fluorescence spectroscopy and calculated by quantum chemical calculations. The compounds exhibit rather small HOMO/LUMO gaps and a remarkable bathochromic shift of luminescence upon protonation, what makes these compounds promising candidates for optoelectronic applications.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"1 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418432","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}
Byunghyuck Jung, Cheong Hoon Park, Seeun Lim, Yunmi Lee
The formal hydroamidation of alkyne is a powerful synthetic method that enables the formation of various α,β‐unsaturated amides. In this article, the efficient formal hydroamidation of terminal and internal alkynes is described, which constitutes the Ni‐catalyzed α‐selective hydroalumination of alkynes and subsequent treatment with isocyanates. This method is gram‐scalable and the synthetic utility is highlighted by the synthesis of a β‐lactam from α‐phenyl acrylamide.
{"title":"Regioselective Formal Hydroamidation of Alkynes: Synthesis of α‐Substituted Acrylamides","authors":"Byunghyuck Jung, Cheong Hoon Park, Seeun Lim, Yunmi Lee","doi":"10.1002/ejoc.202401484","DOIUrl":"https://doi.org/10.1002/ejoc.202401484","url":null,"abstract":"The formal hydroamidation of alkyne is a powerful synthetic method that enables the formation of various α,β‐unsaturated amides. In this article, the efficient formal hydroamidation of terminal and internal alkynes is described, which constitutes the Ni‐catalyzed α‐selective hydroalumination of alkynes and subsequent treatment with isocyanates. This method is gram‐scalable and the synthetic utility is highlighted by the synthesis of a β‐lactam from α‐phenyl acrylamide.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"64 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418433","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}
Xiaojuan Zhou, Xin-Chao Ma, Zhiyang Hong, Jing-Yi Zhang, Rui Wang
Multicomponent reactions (MCRs) have drawn great attention due to their various significant advantages including highly effective, environment‐friendly, and atom‐economic. Developing more efficient and selective MCRs is of great significance to construct chemical libraries of potential functional compounds. On the other hand, supramolecular containers have been successfully applied as novel nanoreactors to mediate diverse organic transformations, and MCRs are included. In this review, examples of supramolecular container mediated MCRs have been summarized. The supramolecular containers include β‐cyclodextrin (β‐CD), γ‐cyclodextrin (γ‐CD), calix[4]arene, self‐assembled Ga(III)‐ligand tetrahedral coordination cage ([Ga4L6]12−), and decanuclear 3d‐4f lanthanide metal‐organic cage ([Zn2Yb8(L)8Cl2]2+). The MCRs cover Hantzsch, Biginelli, Aza‐Darzens, Strecker, and other three‐component reactions. Effects of the supramolecular containers have been illustrated and prospects for the future are also provided.
{"title":"Multicomponent Reactions Mediated by Supramolecular Containers","authors":"Xiaojuan Zhou, Xin-Chao Ma, Zhiyang Hong, Jing-Yi Zhang, Rui Wang","doi":"10.1002/ejoc.202500008","DOIUrl":"https://doi.org/10.1002/ejoc.202500008","url":null,"abstract":"Multicomponent reactions (MCRs) have drawn great attention due to their various significant advantages including highly effective, environment‐friendly, and atom‐economic. Developing more efficient and selective MCRs is of great significance to construct chemical libraries of potential functional compounds. On the other hand, supramolecular containers have been successfully applied as novel nanoreactors to mediate diverse organic transformations, and MCRs are included. In this review, examples of supramolecular container mediated MCRs have been summarized. The supramolecular containers include β‐cyclodextrin (β‐CD), γ‐cyclodextrin (γ‐CD), calix[4]arene, self‐assembled Ga(III)‐ligand tetrahedral coordination cage ([Ga4L6]12−), and decanuclear 3d‐4f lanthanide metal‐organic cage ([Zn2Yb8(L)8Cl2]2+). The MCRs cover Hantzsch, Biginelli, Aza‐Darzens, Strecker, and other three‐component reactions. Effects of the supramolecular containers have been illustrated and prospects for the future are also provided.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"80 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418431","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}
Jiahui Du, Xun Yang, Haiyan Li, Yuxuan Xiao, Ying Yin, Junying Wen, Chan Yang, Ze Tan, Lin Yu
A straightforward and efficient method has been developed for the transformation of aromatic CAr−H bond into CAr−NH₂ via nickel-mediated C−H activation, eliminating the need for additional protection and deprotection steps. This strategy employs 8-aminoquinoline as a directing group and urea as the nitrogen source, a non-toxic, inexpensive, and stable bulk chemical. The reaction exhibits high selectivity, exclusively yielding mono-aminated primary aromatic amines. Furthermore, the protocol is tolerant of a wide range of substrates with various functional groups, producing the corresponding ortho-aminobenzamides in yields ranging from 38% to 73%. The preliminary results indicate the C–H bond cleavage is likely the rate-determining step in the reaction.
{"title":"Urea as an Amine Source to Synthesize Primary Aromatic Amines via Nickel-Mediated C−H Amination","authors":"Jiahui Du, Xun Yang, Haiyan Li, Yuxuan Xiao, Ying Yin, Junying Wen, Chan Yang, Ze Tan, Lin Yu","doi":"10.1002/ejoc.202500087","DOIUrl":"https://doi.org/10.1002/ejoc.202500087","url":null,"abstract":"A straightforward and efficient method has been developed for the transformation of aromatic CAr−H bond into CAr−NH₂ via nickel-mediated C−H activation, eliminating the need for additional protection and deprotection steps. This strategy employs 8-aminoquinoline as a directing group and urea as the nitrogen source, a non-toxic, inexpensive, and stable bulk chemical. The reaction exhibits high selectivity, exclusively yielding mono-aminated primary aromatic amines. Furthermore, the protocol is tolerant of a wide range of substrates with various functional groups, producing the corresponding ortho-aminobenzamides in yields ranging from 38% to 73%. The preliminary results indicate the C–H bond cleavage is likely the rate-determining step in the reaction.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"19 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393828","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}
Qing Luo, Tingting Liu, Linlin Huang, Qianli Li, Wei Lu
The development of phosphinidene precursors capable of releasing free phosphinidenes holds great potential in exploiting their reactivity with small molecules and enthalpically strong bonds. We report the facile cleavage of dichalcogenide bonds, including S‐S, Se‐Se and Te‐Te bonded complexes over the phosphorus center of a bisphosphirane‐fused anthracene (1), which produces a variety of phosphonodichalcogenides (2‐4). We also show the ambiphilic nature of 1. The reaction of 1 with nucleophiles, such as 1,3‐bis(isopropyl)imidazol‐2‐ylidene (IiPr) and 2,6‐diisopropylphenyl isocyanide (DipNC) gives a phosphinidene adduct of IiPr and a 1‐phospha‐3‐azaallene, respectively. Treatment of 1 with trimethylsilyl azide (TMSN3) affords an iminophosphanide, manifesting the nucleophilic nature of 1. These compounds were fully characterized by single‐crystal X‐ray diffraction (SC‐XRD) and spectroscopic analysis.
{"title":"On the Reactivity of Bisphosphirane‐Fused Anthracene towards Dichalcogenide Bonds, IPr Carbene, 2,6‐Diisopropylphenyl Isocyanide and Trimethylsilyl Azide","authors":"Qing Luo, Tingting Liu, Linlin Huang, Qianli Li, Wei Lu","doi":"10.1002/ejoc.202500071","DOIUrl":"https://doi.org/10.1002/ejoc.202500071","url":null,"abstract":"The development of phosphinidene precursors capable of releasing free phosphinidenes holds great potential in exploiting their reactivity with small molecules and enthalpically strong bonds. We report the facile cleavage of dichalcogenide bonds, including S‐S, Se‐Se and Te‐Te bonded complexes over the phosphorus center of a bisphosphirane‐fused anthracene (1), which produces a variety of phosphonodichalcogenides (2‐4). We also show the ambiphilic nature of 1. The reaction of 1 with nucleophiles, such as 1,3‐bis(isopropyl)imidazol‐2‐ylidene (IiPr) and 2,6‐diisopropylphenyl isocyanide (DipNC) gives a phosphinidene adduct of IiPr and a 1‐phospha‐3‐azaallene, respectively. Treatment of 1 with trimethylsilyl azide (TMSN3) affords an iminophosphanide, manifesting the nucleophilic nature of 1. These compounds were fully characterized by single‐crystal X‐ray diffraction (SC‐XRD) and spectroscopic analysis.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"208 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393135","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}
Hao-Tian Wang, Xin-Ting Qin, Bo Jiang, Zhi-Chao Chen, Wei Du, Ying-Chun Chen
Here we demonstrate that a Pt0 complex can function as an efficient π-Lewis base catalyst to increase the nucleophilicity of deactivated heteroarenes upon η2-coordination and resultant π-backdonation, thus enabling asymmetric Friedel−Crafts reaction with electrophiles. A diversity of densely functionalized adducts are produced in high yields with moderate to excellent enantioselectivity. Preliminary frontier molecular orbital (FMO) calculations and in situ 1H NMR analysis support the Pt0 π-Lewis base catalytic mode.
{"title":"A Platinum(0) Complex as π-Lewis Base Catalyst for Asymmetric Friedel−Crafts Reaction","authors":"Hao-Tian Wang, Xin-Ting Qin, Bo Jiang, Zhi-Chao Chen, Wei Du, Ying-Chun Chen","doi":"10.1002/ejoc.202401458","DOIUrl":"https://doi.org/10.1002/ejoc.202401458","url":null,"abstract":"Here we demonstrate that a Pt0 complex can function as an efficient π-Lewis base catalyst to increase the nucleophilicity of deactivated heteroarenes upon η2-coordination and resultant π-backdonation, thus enabling asymmetric Friedel−Crafts reaction with electrophiles. A diversity of densely functionalized adducts are produced in high yields with moderate to excellent enantioselectivity. Preliminary frontier molecular orbital (FMO) calculations and in situ 1H NMR analysis support the Pt0 π-Lewis base catalytic mode.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"41 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393804","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}
Indoles, which are distinguished by their nitrogen-containing heterocyclic structure, play a pivotal role in organic chemistry due to their diverse biological profiles and unique chemical reactivity. In particular, poly-substituted indoles are extensively found in a wide range of natural products, pharmaceuticals, materials, and bioactive compounds. The integration of indoles into multicomponent reactions (MCRs) has emerged as a powerful synthetic strategy, facilitating the construction of these complex poly-substituted indole frameworks from simple precursors. This review highlights the latest advancements in MCRs involving indoles, focusing on innovative methodologies for site-selective synthesis of indole derivatives, catalytic systems, mechanistic insights, and their applications. The review encompasses significant developments from 2014 to 2024 and covers a variety of indole MCRs, including those targeting the C3 position, dual-site reactions at the C2 and C3 positions, and reactions involving the pyrrole and benzene rings of the indole scaffold.
{"title":"Recent Advances in the Multicomponent Reactions of Indoles","authors":"Xiaoxiang Zhang, Xiaohe Lu, Pengyan Zhang, Maoyi Dai, Taoyuan Liang","doi":"10.1002/ejoc.202401446","DOIUrl":"https://doi.org/10.1002/ejoc.202401446","url":null,"abstract":"Indoles, which are distinguished by their nitrogen-containing heterocyclic structure, play a pivotal role in organic chemistry due to their diverse biological profiles and unique chemical reactivity. In particular, poly-substituted indoles are extensively found in a wide range of natural products, pharmaceuticals, materials, and bioactive compounds. The integration of indoles into multicomponent reactions (MCRs) has emerged as a powerful synthetic strategy, facilitating the construction of these complex poly-substituted indole frameworks from simple precursors. This review highlights the latest advancements in MCRs involving indoles, focusing on innovative methodologies for site-selective synthesis of indole derivatives, catalytic systems, mechanistic insights, and their applications. The review encompasses significant developments from 2014 to 2024 and covers a variety of indole MCRs, including those targeting the C3 position, dual-site reactions at the C2 and C3 positions, and reactions involving the pyrrole and benzene rings of the indole scaffold.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"7 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143401906","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}
Peter Gabko, Sergej Šesták, Ján Moncoľ, Maroš Bella
Development of selective Golgi α-mannosidase II inhibitors possessing a modified swainsonine skeleton has recently become a popular field of study due to their great potential in suppressing metastasis. However, most of the studied modifications involve addition of a substituent on the bicycle which makes the synthesis rather complex as five stereogenic centres have to be generated. Inspired by our previously developed synthesis of (5S)-5-benzylswainsonines utilizing a fully stereoselective intramolecular reductive amination, we decided to further investigate the versatility of this strategy by preparing a small collection of simplified analogues bearing only two hydroxy groups, thus eliminating one of the stereogenic centres. This contribution reports a concise synthesis of 5-substituted 1,2-dihydroxyindolizidines and -pyrrolizidines whose key features include small number of steps, high yields and excellent stereoselectivity. The title compounds were also tested for inhibitory activity against a Golgi and a lysosomal α-mannosidase to assess the effects of the substituents, ring size and missing C8-hydroxyl on potency and selectivity.
{"title":"5-Substituted 1,2-Dihydroxyindolizidines and -Pyrrolizidines Related to Swainsonine: Synthesis and Inhibition Study","authors":"Peter Gabko, Sergej Šesták, Ján Moncoľ, Maroš Bella","doi":"10.1002/ejoc.202401307","DOIUrl":"https://doi.org/10.1002/ejoc.202401307","url":null,"abstract":"Development of selective Golgi α-mannosidase II inhibitors possessing a modified swainsonine skeleton has recently become a popular field of study due to their great potential in suppressing metastasis. However, most of the studied modifications involve addition of a substituent on the bicycle which makes the synthesis rather complex as five stereogenic centres have to be generated. Inspired by our previously developed synthesis of (5S)-5-benzylswainsonines utilizing a fully stereoselective intramolecular reductive amination, we decided to further investigate the versatility of this strategy by preparing a small collection of simplified analogues bearing only two hydroxy groups, thus eliminating one of the stereogenic centres. This contribution reports a concise synthesis of 5-substituted 1,2-dihydroxyindolizidines and -pyrrolizidines whose key features include small number of steps, high yields and excellent stereoselectivity. The title compounds were also tested for inhibitory activity against a Golgi and a lysosomal α-mannosidase to assess the effects of the substituents, ring size and missing C8-hydroxyl on potency and selectivity.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"4 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393844","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}
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