Tong Li , Jia-Juan He , Kai-Yu Fan , Long-Wu Ye , Bo Zhou , Xin-Qi Zhu
The Buchner reaction, as an exclusive category of expansive dearomatization, represents a powerful approach for the construction of valuable functionalized cycloheptatrienes in a direct manner from readily available aromatic precursors. However, the traditional Buchner reaction almost relies on using explosive diazo compounds as carbene precursors. Herein, we disclose a copper-catalyzed Buchner reaction through diyne cyclization, and bicycle-fused cycloheptatrienes bearing all carbon quaternary stereogenic centers are obtained in moderate to excellent yields with a broad substrate scope. In addition, norcaradiene derivatives can also be selectively produced by substrate control through a phenyl cyclopropanation reaction, thus constituting a copper-catalyzed controllable cyclization of diynes.
b chner反应，作为一种独特的膨胀脱芳反应，代表了一种从现成的芳香前体直接构建有价值的功能化环庚三烯的有力方法。然而，传统的b chner反应几乎依赖于使用爆炸性重氮化合物作为碳前体。在此，我们通过双炔环化揭示了铜催化的b chner反应，并以中等至优异的产率和广泛的底物范围获得了含有所有碳的四元立体中心的环庚三烯。此外，还可以通过苯基环丙烷化反应控制底物选择性地生成去甲二烯衍生物，从而构成铜催化的二炔可控环化反应。
{"title":"Copper-catalyzed Buchner reaction and phenyl cyclopropanation through diyne cyclization†","authors":"Tong Li , Jia-Juan He , Kai-Yu Fan , Long-Wu Ye , Bo Zhou , Xin-Qi Zhu","doi":"10.1039/d4qo02371d","DOIUrl":"10.1039/d4qo02371d","url":null,"abstract":"<div><div>The Buchner reaction, as an exclusive category of expansive dearomatization, represents a powerful approach for the construction of valuable functionalized cycloheptatrienes in a direct manner from readily available aromatic precursors. However, the traditional Buchner reaction almost relies on using explosive diazo compounds as carbene precursors. Herein, we disclose a copper-catalyzed Buchner reaction through diyne cyclization, and bicycle-fused cycloheptatrienes bearing all carbon quaternary stereogenic centers are obtained in moderate to excellent yields with a broad substrate scope. In addition, norcaradiene derivatives can also be selectively produced by substrate control through a phenyl cyclopropanation reaction, thus constituting a copper-catalyzed controllable cyclization of diynes.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 6","pages":"Pages 1966-1972"},"PeriodicalIF":0.0,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/qo/d4qo02371d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142991925","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Anil Rangnath Pawar , Sabina Yashmin , Abu Taleb Khan
A novel metal-free synthetic method is presented for 2-arylchromeno[2,3,4,5-lmna]phenanthridines from the one-pot reaction of aryl amine, aromatic aldehyde and cyclic ketone in the presence of 30 mol% (±)-CSA. This protocol efficiently exploits DMSO as a solvent and a source of –O– for the installation of a regioselective keto functionality in the key reaction intermediate 5-aryl-3,4-dihydrobenzo[a]phenanthridin-1(2H)-one () through multicomponent reactions. Due to its rigid structure, facilitates further domino reactions such as 6πe electrocyclization and aromatization, which have not been studied before. The sophisticated aspect of this approach lies in its ability to create two CC, one CN, and two C–O bonds simultaneously in a single step without requiring a base or an activator for the oxygenation process.
{"title":"Synthesis of 2-arylchromeno[2,3,4,5-lmna]phenanthridines through a sequential multicomponent assembly, oxygenation and 6πe electrocyclization reactions†","authors":"Anil Rangnath Pawar , Sabina Yashmin , Abu Taleb Khan","doi":"10.1039/d4qo02067g","DOIUrl":"10.1039/d4qo02067g","url":null,"abstract":"<div><div>A novel metal-free synthetic method is presented for 2-arylchromeno[2,3,4,5-<em>lmna</em>]phenanthridines from the one-pot reaction of aryl amine, aromatic aldehyde and cyclic ketone in the presence of 30 mol% (±)-CSA. This protocol efficiently exploits DMSO as a solvent and a source of –O– for the installation of a regioselective keto functionality in the key reaction intermediate 5-aryl-3,4-dihydrobenzo[<em>a</em>]phenanthridin-1(2<em>H</em>)-one () through multicomponent reactions. Due to its rigid structure, facilitates further domino reactions such as 6πe electrocyclization and aromatization, which have not been studied before. The sophisticated aspect of this approach lies in its ability to create two CC, one CN, and two C–O bonds simultaneously in a single step without requiring a base or an activator for the oxygenation process.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 6","pages":"Pages 1833-1841"},"PeriodicalIF":0.0,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142937402","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mohammad Asadpour , Edson Leonardo Scarpa de Souza , Anke Spannenberg , Carlos Roque Duarte Correia , Helfried Neumann , Matthias Beller
A new class of amino acids, so-called fatty amino acids, which integrate the typical structural motif of another important class of natural products, fatty acids, is presented. By applying palladium-catalyzed amidocarbonylation, diverse new N-acyl fatty amino acids are synthesized in one step in a 100% atom-efficient manner. Utilizing a small amount (0.5 mol%) of simple commercial Pd(OAc)2, the desired products can be synthesized in good to high yields, up to multi-g-scale. The shown products represent a combination of two essential classes of natural products and provide new bio-based building blocks with potential for many applications.
{"title":"Combination of the structural components of amino acids with fatty acids: access to an unknown class of “fatty” α-amino acids by palladium-catalyzed amidocarbonylation†","authors":"Mohammad Asadpour , Edson Leonardo Scarpa de Souza , Anke Spannenberg , Carlos Roque Duarte Correia , Helfried Neumann , Matthias Beller","doi":"10.1039/d4qo01127a","DOIUrl":"10.1039/d4qo01127a","url":null,"abstract":"<div><div>A new class of amino acids, so-called fatty amino acids, which integrate the typical structural motif of another important class of natural products, fatty acids, is presented. By applying palladium-catalyzed amidocarbonylation, diverse new <em>N</em>-acyl fatty amino acids are synthesized in one step in a 100% atom-efficient manner. Utilizing a small amount (0.5 mol%) of simple commercial Pd(OAc)<sub>2</sub>, the desired products can be synthesized in good to high yields, up to multi-g-scale. The shown products represent a combination of two essential classes of natural products and provide new bio-based building blocks with potential for many applications.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 6","pages":"Pages 1748-1753"},"PeriodicalIF":0.0,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/qo/d4qo01127a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143020529","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xingxing Yang , Yourong Pan , Cheng Ren , Chengrui Hu , Feng Wan , Hongliang Duan , Chengxi Li
ortho-Alkylated phenols are widely found in natural products and bioactive compounds. Here we have developed a mild, transition-metal-free approach for the C(sp3)–C(sp2) cross-coupling of alkenyl boronic acids with secondary alcohols via neighboring group activation, furnishing a series of ortho-allylphenols. The C(sp3)–hydroxyl group was activated through intramolecular interactions with ortho-phenolic functional groups (triflyl, tert-butoxycarbonyl, phosphoryl, and cyclic carbonate). This method exhibits good substrate compatibility, allowing for the efficient synthesis of ortho-allyl phenols and their subsequent transformation into high-value scaffolds.
{"title":"Transition-metal-free C(sp3)–C(sp2) couplings with secondary alcohols and boronic acids via neighboring group activation†","authors":"Xingxing Yang , Yourong Pan , Cheng Ren , Chengrui Hu , Feng Wan , Hongliang Duan , Chengxi Li","doi":"10.1039/d4qo02061h","DOIUrl":"10.1039/d4qo02061h","url":null,"abstract":"<div><div> <em>ortho</em>-Alkylated phenols are widely found in natural products and bioactive compounds. Here we have developed a mild, transition-metal-free approach for the C(sp<sup>3</sup>)–C(sp<sup>2</sup>) cross-coupling of alkenyl boronic acids with secondary alcohols <em>via</em> neighboring group activation, furnishing a series of <em>ortho</em>-allylphenols. The C(sp<sup>3</sup>)–hydroxyl group was activated through intramolecular interactions with <em>ortho</em>-phenolic functional groups (triflyl, <em>tert</em>-butoxycarbonyl, phosphoryl, and cyclic carbonate). This method exhibits good substrate compatibility, allowing for the efficient synthesis of <em>ortho</em>-allyl phenols and their subsequent transformation into high-value scaffolds.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 6","pages":"Pages 1786-1791"},"PeriodicalIF":0.0,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142936535","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Peng-Jun Zhou , Ze-Yu Zhao , Sha Chen , Gong-Pu Luo , Jin-Xin Zhu , Xu-Wen Li , Yeun-Mun Choo , Mark T. Hamann , Juan Xiong , Jin-Feng Hu
As a new chemical class of bis-diterpene heterodimers, spiroamentotaxols A–D () are characterized by a complex 6/6/6/5/6/6/6/6 spiro-octacyclic ring system, which is likely biogenetically derived from a Diels–Alder [4 + 2] cycloaddition between an ent-kaurene and a C20-norabietane. The spiroamentotaxols possess a distinctive spiro[bicyclo[3.2.1]octane-7,2′-bicyclo[2.2.2]octene] motif. Through the application of molecular ion networking (MoIN), these intermolecular Diels–Alder isomers were isolated from the renewable twigs and needles of the endangered Chinese conifer Amentotaxus yunnanensis. Their chemical structures were elucidated using spectroscopic methods, electronic circular dichroism calculations, and X-ray diffraction analysis. From a structural diversity perspective, two semi-synthetic analogs, namely, 7′-deoxy-6′-en-spiroamentotaxol A () and 7′-deoxy-spiroamentotaxol A (), were synthesized from the relatively major compound . These spiro-polycyclic compounds were evaluated for their in vitro anti-inflammatory and anticancer activities. In particular, compound attenuated inflammation in both RAW 264.7 macrophage and BV2 microglial cells at a non-toxic concentration of 20 μM, with the lipopolysaccharide (LPS)-induced nitric oxide production inhibition rates of 46.66% and 32.37%, respectively. exhibited efficacy against a panel of human cancer cell lines (A549, MCF7, HCT116, RKO, and HepG2), with IC50 values ranging from 6.27 to 14.10 μM. In the case of HCT116 cells, specifically influenced cell-cycle progression at the G2 phase and induced apoptosis. The findings highlight the importance of conserving plant species diversity as a means to sustain chemical diversity and serve as a potential source of new therapeutic agents for cancer treatment.
{"title":"Spiroamentotaxols A–D: unprecedented 6/6/6/5/6/6/6/6 spiro-octacyclic bis-diterpene heterodimers from the endangered conifer Amentotaxus yunnanensis and their bioactivities†","authors":"Peng-Jun Zhou , Ze-Yu Zhao , Sha Chen , Gong-Pu Luo , Jin-Xin Zhu , Xu-Wen Li , Yeun-Mun Choo , Mark T. Hamann , Juan Xiong , Jin-Feng Hu","doi":"10.1039/d4qo02210f","DOIUrl":"10.1039/d4qo02210f","url":null,"abstract":"<div><div>As a new chemical class of bis-diterpene heterodimers, spiroamentotaxols A–D () are characterized by a complex 6/6/6/5/6/6/6/6 spiro-octacyclic ring system, which is likely biogenetically derived from a Diels–Alder [4 + 2] cycloaddition between an <em>ent</em>-kaurene and a C<sub>20</sub>-norabietane. The spiroamentotaxols possess a distinctive spiro[bicyclo[3.2.1]octane-7,2′-bicyclo[2.2.2]octene] motif. Through the application of molecular ion networking (MoIN), these intermolecular Diels–Alder isomers were isolated from the renewable twigs and needles of the endangered Chinese conifer <em>Amentotaxus yunnanensis</em>. Their chemical structures were elucidated using spectroscopic methods, electronic circular dichroism calculations, and X-ray diffraction analysis. From a structural diversity perspective, two semi-synthetic analogs, namely, 7′-deoxy-6′-en-spiroamentotaxol A () and 7′-deoxy-spiroamentotaxol A (), were synthesized from the relatively major compound . These spiro-polycyclic compounds were evaluated for their <em>in vitro</em> anti-inflammatory and anticancer activities. In particular, compound attenuated inflammation in both RAW 264.7 macrophage and BV2 microglial cells at a non-toxic concentration of 20 μM, with the lipopolysaccharide (LPS)-induced nitric oxide production inhibition rates of 46.66% and 32.37%, respectively. exhibited efficacy against a panel of human cancer cell lines (A549, MCF7, HCT116, RKO, and HepG2), with IC<sub>50</sub> values ranging from 6.27 to 14.10 μM. In the case of HCT116 cells, specifically influenced cell-cycle progression at the G2 phase and induced apoptosis. The findings highlight the importance of conserving plant species diversity as a means to sustain chemical diversity and serve as a potential source of new therapeutic agents for cancer treatment.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 6","pages":"Pages 1893-1904"},"PeriodicalIF":0.0,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990000","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Gang Wang , Yu-Heng Zeng , Qian-Yu Jiang , Jia-Yi Chen , Rong Zhou , Huai-Bo Zou
α-Amino nitriles and succinonitriles represent two crucial classes of cyano-containing compounds with significant applications. Herein, we reported for the first time a divergent synthesis of α-amino nitriles and asymmetric α-amino succinonitriles through mono-, di- and tricyanomethylation between primary amines and diazoacetonitrile. This reaction was catalyzed by (TPP)Fe(iii)Cl or PcFe(iii)Cl in either dichloromethane (DCM) alone or a mixed solvent of DCM and acetonitrile at room temperature. The combination of mono- and dicyanomethylation is a new solvent-controlled divergent synthesis approach. Both di- and tricyanomethylation represent novel transformation types in metalloradical catalysis, constructing one C–C bond and multiple (two or three) C–N bonds in one-pot. This approach is distinctly different from the conventional N–H insertion between amines and diazo reagents. Furthermore, the divergent synthesis enables gram-scale preparation of three typical compounds. Mechanistically, monocyanomethylation proceeds via the N–H insertion pathway. For di- and tricyanomethylation, the mechanism involves homodimerization of the iron(iv)–acetonitrile radical, derived from the reaction between diazoacetonitrile and (TPP)Fe(iii)Cl coordinated by bis(amines) or PcFe(iii)Cl. Subsequently, monoamination occurs through the attack of one amine molecule on a carbon atom of the formed C–C bond.
{"title":"Iron(iii)-catalyzed mono-, di- and tricyanomethylation of primary amines with diazoacetonitrile: construction of α-amino acetonitriles and asymmetric α-amino succinonitriles†","authors":"Gang Wang , Yu-Heng Zeng , Qian-Yu Jiang , Jia-Yi Chen , Rong Zhou , Huai-Bo Zou","doi":"10.1039/d4qo02218a","DOIUrl":"10.1039/d4qo02218a","url":null,"abstract":"<div><div>α-Amino nitriles and succinonitriles represent two crucial classes of cyano-containing compounds with significant applications. Herein, we reported for the first time a divergent synthesis of α-amino nitriles and asymmetric α-amino succinonitriles through mono-, di- and tricyanomethylation between primary amines and diazoacetonitrile. This reaction was catalyzed by (TPP)Fe(<span>iii</span>)Cl or PcFe(<span>iii</span>)Cl in either dichloromethane (DCM) alone or a mixed solvent of DCM and acetonitrile at room temperature. The combination of mono- and dicyanomethylation is a new solvent-controlled divergent synthesis approach. Both di- and tricyanomethylation represent novel transformation types in metalloradical catalysis, constructing one C–C bond and multiple (two or three) C–N bonds in one-pot. This approach is distinctly different from the conventional N–H insertion between amines and diazo reagents. Furthermore, the divergent synthesis enables gram-scale preparation of three typical compounds. Mechanistically, monocyanomethylation proceeds <em>via</em> the N–H insertion pathway. For di- and tricyanomethylation, the mechanism involves homodimerization of the iron(<span>iv</span>)–acetonitrile radical, derived from the reaction between diazoacetonitrile and (TPP)Fe(<span>iii</span>)Cl coordinated by bis(amines) or PcFe(<span>iii</span>)Cl. Subsequently, monoamination occurs through the attack of one amine molecule on a carbon atom of the formed C–C bond.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 6","pages":"Pages 1992-2003"},"PeriodicalIF":0.0,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142992609","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yaoluo Hu , Ya Hong , Yuting Zheng , Yi Huang , Jixiang Chen , Xingxing Wu
Phenanthrenequinones (PQs) are extensively studied in synthetic chemistry and materials science, exhibiting noteworthy biological activities essential for drug discovery. The development of efficient synthetic methods for PQ preparation has thus garnered significant attention, particularly through metal-catalyzed transformations. In this study, we present an N-heterocyclic carbene organocatalytic approach that enables the rapid construction of a diverse range of PQs and their derivatives without the need for stoichiometric oxidants or metal mediators. Mechanistically, the initial carbene-catalyzed formation of a benzoin adduct between an aldehyde and ester is critical for initiating a subsequent annulation reaction involving an aryl radical species. Our method represents the first example of the direct construction of PQ frameworks from simple starting materials by means of small-molecule catalysts. Furthermore, the catalytically obtained PQ products exhibit notable antimicrobial activity against common plant pathogens, offering promising potential for agrochemical development.
{"title":"Synthesis of antimicrobial active 9,10-phenanthrenequinones by carbene organocatalytic tandem reactions†","authors":"Yaoluo Hu , Ya Hong , Yuting Zheng , Yi Huang , Jixiang Chen , Xingxing Wu","doi":"10.1039/d4qo02193b","DOIUrl":"10.1039/d4qo02193b","url":null,"abstract":"<div><div>Phenanthrenequinones (PQs) are extensively studied in synthetic chemistry and materials science, exhibiting noteworthy biological activities essential for drug discovery. The development of efficient synthetic methods for PQ preparation has thus garnered significant attention, particularly through metal-catalyzed transformations. In this study, we present an N-heterocyclic carbene organocatalytic approach that enables the rapid construction of a diverse range of PQs and their derivatives without the need for stoichiometric oxidants or metal mediators. Mechanistically, the initial carbene-catalyzed formation of a benzoin adduct between an aldehyde and ester is critical for initiating a subsequent annulation reaction involving an aryl radical species. Our method represents the first example of the direct construction of PQ frameworks from simple starting materials by means of small-molecule catalysts. Furthermore, the catalytically obtained PQ products exhibit notable antimicrobial activity against common plant pathogens, offering promising potential for agrochemical development.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 6","pages":"Pages 1778-1785"},"PeriodicalIF":0.0,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981322","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Changhee Park , Seyun Gi , Seongkyeong Yoon , Seong Jung Kwon , Sunggi Lee
Amine carboxyborane enabled efficient halogen atom transfer (XAT) with 1°, 2°, and 3° alkyl bromides, resulting in Giese addition products with various electron-deficient double bonds. Moreover, direct addition of several boryl radicals was also possible using several ligated carboxyboranes.
{"title":"The Giese reaction of alkyl bromides using amine carboxyboranes†","authors":"Changhee Park , Seyun Gi , Seongkyeong Yoon , Seong Jung Kwon , Sunggi Lee","doi":"10.1039/d4qo02325k","DOIUrl":"10.1039/d4qo02325k","url":null,"abstract":"<div><div>Amine carboxyborane enabled efficient halogen atom transfer (XAT) with 1°, 2°, and 3° alkyl bromides, resulting in Giese addition products with various electron-deficient double bonds. Moreover, direct addition of several boryl radicals was also possible using several ligated carboxyboranes.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 6","pages":"Pages 1874-1878"},"PeriodicalIF":0.0,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142937399","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Huilan Zhang , Michael Ho-Yeung Chan , Jonathan Lam , Ming-Yi Leung , Lixin Wu , Vivian Wing-Wah Yam
A new class of water-soluble amphiphilic Schiff base-containing platinum(ii) complexes with dendritic triethylene glycol units has been investigated to show self-assembly properties by the balance of multiple noncovalent interactions including hydrophobic, intermolecular Pt⋯Pt and π–π stacking interactions in water or DMSO–water solutions, accompanied by drastic spectroscopic changes. The UV–vis spectra have been recorded, and the electronic structures and intermolecular Pt⋯Pt interactions have been confirmed by computational studies and non-covalent interaction (NCI) analysis of the dimer of the complex. These complexes have been found to exhibit a cooperative self-assembly mechanism, in which the molecules were stacked in a head-to-tail arrangement in a slightly staggered fashion. Additionally, the length of the alkoxy chains has been found to show a significant effect on the extent of Pt⋯Pt and π–π stacking interactions and the stability of their self-assembled aggregates. Under the influence of temperature, this class of Schiff base-containing platinum(ii) complexes has been shown to exhibit an unexpected hysteresis effect and unusual thermo-responsive behavior accompanied by morphological transformation. This work represents a rare example of a systematic study on the self-assembly properties of water-soluble platinum(ii) Schiff base complexes induced by molecular hydrophobicity, solvation and temperature. It provides an in-depth insight into the rational molecular design for the construction of supramolecular architectures and potential advances in stimuli-responsive probes.
{"title":"Solvation and temperature-modulated supramolecular assembly of amphiphilic water-soluble Schiff base-containing platinum(ii) complexes†‡","authors":"Huilan Zhang , Michael Ho-Yeung Chan , Jonathan Lam , Ming-Yi Leung , Lixin Wu , Vivian Wing-Wah Yam","doi":"10.1039/d4qo02258k","DOIUrl":"10.1039/d4qo02258k","url":null,"abstract":"<div><div>A new class of water-soluble amphiphilic Schiff base-containing platinum(<span>ii</span>) complexes with dendritic triethylene glycol units has been investigated to show self-assembly properties by the balance of multiple noncovalent interactions including hydrophobic, intermolecular Pt⋯Pt and π–π stacking interactions in water or DMSO–water solutions, accompanied by drastic spectroscopic changes. The UV–vis spectra have been recorded, and the electronic structures and intermolecular Pt⋯Pt interactions have been confirmed by computational studies and non-covalent interaction (NCI) analysis of the dimer of the complex. These complexes have been found to exhibit a cooperative self-assembly mechanism, in which the molecules were stacked in a head-to-tail arrangement in a slightly staggered fashion. Additionally, the length of the alkoxy chains has been found to show a significant effect on the extent of Pt⋯Pt and π–π stacking interactions and the stability of their self-assembled aggregates. Under the influence of temperature, this class of Schiff base-containing platinum(<span>ii</span>) complexes has been shown to exhibit an unexpected hysteresis effect and unusual thermo-responsive behavior accompanied by morphological transformation. This work represents a rare example of a systematic study on the self-assembly properties of water-soluble platinum(<span>ii</span>) Schiff base complexes induced by molecular hydrophobicity, solvation and temperature. It provides an in-depth insight into the rational molecular design for the construction of supramolecular architectures and potential advances in stimuli-responsive probes.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 6","pages":"Pages 1733-1747"},"PeriodicalIF":0.0,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385458","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Haijian Wu , Manman Sun , Jing Zhang , Zhiming Wang , Jianguo Yang , Gangguo Zhu
A formal [2π + 2σ] cycloaddition of BCBs with p-QMs has been developed using a small amount of HFIP (2 M) as the solvent without an additional catalyst, in which HFIP also served as a H-bond donor and a cationic stabilizer. This protocol enables the rapid construction of spiro-BCHs in good to excellent yields with a broad substrate scope. Easy scale-up synthesis, potential applications in the modification of bioactive products, mild reaction conditions and simple operation are its practical advantages.
{"title":"HFIP-promoted formal [2π + 2σ] cycloaddition of para-quinone methides with bicyclo[1.1.0]butanes: an approach towards spiro-bicyclo[2.1.1]hexanes†","authors":"Haijian Wu , Manman Sun , Jing Zhang , Zhiming Wang , Jianguo Yang , Gangguo Zhu","doi":"10.1039/d4qo02226b","DOIUrl":"10.1039/d4qo02226b","url":null,"abstract":"<div><div>A formal [2π + 2σ] cycloaddition of BCBs with <em>p</em>-QMs has been developed using a small amount of HFIP (2 M) as the solvent without an additional catalyst, in which HFIP also served as a H-bond donor and a cationic stabilizer. This protocol enables the rapid construction of spiro-BCHs in good to excellent yields with a broad substrate scope. Easy scale-up synthesis, potential applications in the modification of bioactive products, mild reaction conditions and simple operation are its practical advantages.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 6","pages":"Pages 1951-1957"},"PeriodicalIF":0.0,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990904","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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