Pub Date : 2024-09-23DOI: 10.31635/ccschem.024.202404559
Yaru Gao, Guorong Hong, Lei Zhang, Ke-Yin Ye, Jiajia Cheng, Bin-Miao Yang, Yu Zhao
We present here a catalytic enantioconvergent amination of alcohols for efficient access to chiral C2- and C3-substituted benzomorpholines. The racemic amino alcohol substrates of different substitution patterns, which are readily available from a common precursor, can be converted to the enantioenriched heterocycles in a highly atom- and step-economical fashion. In particular, an unprecedented asymmetric amination of racemic primary alcohols via dynamic kinetic resolution is achieved under cooperative iridium/iron catalysis, resulting in highly enantioenriched C2-substituted benzomorpholines that are difficult to access otherwise.
{"title":"Asymmetric Amination of Primary Alcohols via Dynamic Kinetic Resolution: Enantioconvergent Access to Chiral Benzomorpholines","authors":"Yaru Gao, Guorong Hong, Lei Zhang, Ke-Yin Ye, Jiajia Cheng, Bin-Miao Yang, Yu Zhao","doi":"10.31635/ccschem.024.202404559","DOIUrl":"https://doi.org/10.31635/ccschem.024.202404559","url":null,"abstract":"<p>We present here a catalytic enantioconvergent amination of alcohols for efficient access to chiral C2- and C3-substituted benzomorpholines. The racemic amino alcohol substrates of different substitution patterns, which are readily available from a common precursor, can be converted to the enantioenriched heterocycles in a highly atom- and step-economical fashion. In particular, an unprecedented asymmetric amination of racemic primary alcohols via dynamic kinetic resolution is achieved under cooperative iridium/iron catalysis, resulting in highly enantioenriched C2-substituted benzomorpholines that are difficult to access otherwise.</p>","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"9 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142313984","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
With the blossom of DNA encoded library (DEL) and nucleic acid aptamer techniques, DNA-compatible reactions draw increasing attention in both the pharmaceutical industry and academia. In this regard, the incorporation of organosulfur scaffolds on DNA via the Csp2–S bond exhibits advantages but remains underrepresented. Herein, we report a mild and efficient photoredox atom transfer radical addition (ATRA) to terminal and internal alkynes with thiosulfonates catalyzed by organic photocatalyst, furnishing a wide array of E-β-arylthiol-vinyl sulfones with excellent regio- and stereoselectivity. Mechanistic investigations demonstrate that sulfonyl radical likely served as the key intermediate in this transformation. Leveraging the broad functional group tolerance and the mild and biofriendly conditions, this protocol could be adapted to simultaneously install sulfones and sulfides on DNA. More importantly, a redox-responsive fluorescent probe (10-ethyl-2-sulfonate-acridone, ESAC) could be conveniently introduced on two commonly used aptamers (AS1411 and Sgc8c), allowing their subsequent imaging studies across a series of human tumor cell lines. Remarkably, the process of ESAC-aptamers entering the cells was captured by both confocal microscopy and flow cytometry techniques, whereby most of the ESAC-aptamers exhibited green fluorescence after their cellular uptake, with the small portion remaining in the outer membrane emitting blue fluorescence.
随着DNA编码文库（DEL）和核酸适配体技术的蓬勃发展，DNA兼容反应越来越受到制药业和学术界的关注。在这方面，通过 Csp2-S 键在 DNA 上结合有机硫支架具有优势，但仍未得到广泛应用。在此，我们报告了一种温和、高效的光氧化原子转移自由基加成（ATRA）方法，在有机光催化剂的催化下，将硫代磺酸盐与末端和内部炔烃进行加成，从而以优异的区域和立体选择性生成了多种 E-β-芳基硫醇-乙烯基砜。机理研究表明，磺酰基可能是这一转化过程中的关键中间体。利用其广泛的官能团耐受性以及温和的生物友好型条件，该方案可同时在 DNA 上安装砜和硫化物。更重要的是，氧化还原反应荧光探针（10-乙基-2-磺酸-吖啶酮，ESAC）可以方便地引入到两种常用的适配体（AS1411 和 Sgc8c）上，从而可以对一系列人类肿瘤细胞系进行后续成像研究。值得注意的是，共聚焦显微镜和流式细胞仪技术都捕捉到了ESAC-适配体进入细胞的过程，其中大部分ESAC-适配体在被细胞吸收后发出绿色荧光，小部分留在外膜上的ESAC-适配体则发出蓝色荧光。
{"title":"DNA-Compatible Photoredox Atom Transfer Radical Addition to Alkynes with Thiosulfonates","authors":"Cong Wang, Yinghui Lu, Zhiyuan Peng, Chi Zhang, Qingchao Liu, Xue-Qiang Wang, Tiezheng Jia","doi":"10.31635/ccschem.024.202404703","DOIUrl":"https://doi.org/10.31635/ccschem.024.202404703","url":null,"abstract":"<p>With the blossom of DNA encoded library (DEL) and nucleic acid aptamer techniques, DNA-compatible reactions draw increasing attention in both the pharmaceutical industry and academia. In this regard, the incorporation of organosulfur scaffolds on DNA via the Csp<sup>2</sup>–S bond exhibits advantages but remains underrepresented. Herein, we report a mild and efficient photoredox atom transfer radical addition (ATRA) to terminal and internal alkynes with thiosulfonates catalyzed by organic photocatalyst, furnishing a wide array of <i>E</i>-β-arylthiol-vinyl sulfones with excellent regio- and stereoselectivity. Mechanistic investigations demonstrate that sulfonyl radical likely served as the key intermediate in this transformation. Leveraging the broad functional group tolerance and the mild and biofriendly conditions, this protocol could be adapted to simultaneously install sulfones and sulfides on DNA. More importantly, a redox-responsive fluorescent probe (10-ethyl-2-sulfonate-acridone, ESAC) could be conveniently introduced on two commonly used aptamers (AS1411 and Sgc8c), allowing their subsequent imaging studies across a series of human tumor cell lines. Remarkably, the process of ESAC-aptamers entering the cells was captured by both confocal microscopy and flow cytometry techniques, whereby most of the ESAC-aptamers exhibited green fluorescence after their cellular uptake, with the small portion remaining in the outer membrane emitting blue fluorescence.</p>","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"1 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142313982","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-23DOI: 10.31635/ccschem.024.202404670
Yang Qu, Rong Sun, Bing-Wu Wang, Song Gao
<p>Combining spin crossover (SCO) and fluorescence properties could respond to multiple physical stimulus and is meaningful for the development of switches and imaging tools. In this work, we present a new family of neutral mononuclear iron(II) complexes, denoted as Fe(<b xmlns:bkstg="http://www.atypon.com/backstage-ns" xmlns:fn="http://www.w3.org/2005/xpath-functions" xmlns:pxje="java:com.atypon.frontend.services.impl.PassportXslJavaExtentions" xmlns:urlutil="java:com.atypon.literatum.customization.UrlUtil" xmlns:xlink="http://www.w3.org/1999/xlink"> <bold>L</bold></b><sup>1–3</sup>)<sub>2</sub> and Fe(<b xmlns:bkstg="http://www.atypon.com/backstage-ns" xmlns:fn="http://www.w3.org/2005/xpath-functions" xmlns:pxje="java:com.atypon.frontend.services.impl.PassportXslJavaExtentions" xmlns:urlutil="java:com.atypon.literatum.customization.UrlUtil" xmlns:xlink="http://www.w3.org/1999/xlink"> <bold>L</bold></b><sup>3</sup>)<sub>2</sub>·CH<sub>2</sub>Cl<sub>2</sub> with N<sub>4</sub>O<sub>2</sub> donor sets. These complexes were synthesized employing a series of tridentate Schiff base ligands, which contain an ethynyl group (H<b xmlns:bkstg="http://www.atypon.com/backstage-ns" xmlns:fn="http://www.w3.org/2005/xpath-functions" xmlns:pxje="java:com.atypon.frontend.services.impl.PassportXslJavaExtentions" xmlns:urlutil="java:com.atypon.literatum.customization.UrlUtil" xmlns:xlink="http://www.w3.org/1999/xlink"> <bold>L</bold></b><sup>1–3</sup> = 3-ethynyl-<i>N</i>′-((4-methylpyridin-2-yl)methylene)benzohydrazide (<b xmlns:bkstg="http://www.atypon.com/backstage-ns" xmlns:fn="http://www.w3.org/2005/xpath-functions" xmlns:pxje="java:com.atypon.frontend.services.impl.PassportXslJavaExtentions" xmlns:urlutil="java:com.atypon.literatum.customization.UrlUtil" xmlns:xlink="http://www.w3.org/1999/xlink"> <bold>4MePAH-3EyBHZ</bold></b>, H<b xmlns:bkstg="http://www.atypon.com/backstage-ns" xmlns:fn="http://www.w3.org/2005/xpath-functions" xmlns:pxje="java:com.atypon.frontend.services.impl.PassportXslJavaExtentions" xmlns:urlutil="java:com.atypon.literatum.customization.UrlUtil" xmlns:xlink="http://www.w3.org/1999/xlink"> <bold>L</bold></b><sup>1</sup>), 3-ethynyl-<i>N</i>′-((4-methoxylpyridin-2-yl)methylene)benzohydrazide (<b xmlns:bkstg="http://www.atypon.com/backstage-ns" xmlns:fn="http://www.w3.org/2005/xpath-functions" xmlns:pxje="java:com.atypon.frontend.services.impl.PassportXslJavaExtentions" xmlns:urlutil="java:com.atypon.literatum.customization.UrlUtil" xmlns:xlink="http://www.w3.org/1999/xlink"> <bold>4OMePAH-3EyBHZ</bold></b>, H<b xmlns:bkstg="http://www.atypon.com/backstage-ns" xmlns:fn="http://www.w3.org/2005/xpath-functions" xmlns:pxje="java:com.atypon.frontend.services.impl.PassportXslJavaExtentions" xmlns:urlutil="java:com.atypon.literatum.customization.UrlUtil" xmlns:xlink="http://www.w3.org/1999/xlink"> <bold>L</bold></b><sup>2</sup>), 3-ethynyl-<i>N</i>′-((5-methylpyridin-2-yl)methylene)benzohydrazide (<b xmlns:bkstg="http://www.atypon.com/backstage
{"title":"Fluorescence Emission Modulation of Alkynyl-Functionalized Iron(II) Spin-Crossover Complexes","authors":"Yang Qu, Rong Sun, Bing-Wu Wang, Song Gao","doi":"10.31635/ccschem.024.202404670","DOIUrl":"https://doi.org/10.31635/ccschem.024.202404670","url":null,"abstract":"<p>Combining spin crossover (SCO) and fluorescence properties could respond to multiple physical stimulus and is meaningful for the development of switches and imaging tools. In this work, we present a new family of neutral mononuclear iron(II) complexes, denoted as Fe(<b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\">\u0000<bold>L</bold></b><sup>1–3</sup>)<sub>2</sub> and Fe(<b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\">\u0000<bold>L</bold></b><sup>3</sup>)<sub>2</sub>·CH<sub>2</sub>Cl<sub>2</sub> with N<sub>4</sub>O<sub>2</sub> donor sets. These complexes were synthesized employing a series of tridentate Schiff base ligands, which contain an ethynyl group (H<b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\">\u0000<bold>L</bold></b><sup>1–3</sup> = 3-ethynyl-<i>N</i>′-((4-methylpyridin-2-yl)methylene)benzohydrazide (<b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\">\u0000<bold>4MePAH-3EyBHZ</bold></b>, H<b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\">\u0000<bold>L</bold></b><sup>1</sup>), 3-ethynyl-<i>N</i>′-((4-methoxylpyridin-2-yl)methylene)benzohydrazide (<b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\">\u0000<bold>4OMePAH-3EyBHZ</bold></b>, H<b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\">\u0000<bold>L</bold></b><sup>2</sup>), 3-ethynyl-<i>N</i>′-((5-methylpyridin-2-yl)methylene)benzohydrazide (<b xmlns:bkstg=\"http://www.atypon.com/backstage","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"120 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142313983","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-16DOI: 10.31635/ccschem.024.202404699
CCS Chemistry, Ahead of Print.
CCS Chemistry, Ahead of Print.
{"title":"Generation and Application of Silyl Acyl Radicals: Facile and Metal-Free Access to Acylsilanes","authors":"","doi":"10.31635/ccschem.024.202404699","DOIUrl":"https://doi.org/10.31635/ccschem.024.202404699","url":null,"abstract":"CCS Chemistry, Ahead of Print.<br/>","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"22 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142235215","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-16DOI: 10.31635/ccschem.024.202404423
CCS Chemistry, Ahead of Print.
CCS Chemistry, Ahead of Print.
{"title":"Scalable Amorphous NiFe(OH)x/Fe/Graphene Bifunctional Electrocatalyst via Solution-Corrosion for Water Splitting","authors":"","doi":"10.31635/ccschem.024.202404423","DOIUrl":"https://doi.org/10.31635/ccschem.024.202404423","url":null,"abstract":"CCS Chemistry, Ahead of Print.<br/>","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"27 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142235217","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-16DOI: 10.31635/ccschem.024.202404213
Hu Yang, Su-Kao Peng, Wenbin Chen, Dong Luo, Shibo Xi, Shuai Lu, Yong-Liang Huang, De-Bo Hao, Bincheng Cai, Heng Wang, Mo Xie, Ming-De Li, Xiaopeng Li, Guo-Hong Ning, Dan Li
<p>The synthesis of helical nanostructures with advanced functions from atomically precise building blocks is attractive, but remains a significant challenge. In this work, we report two atomically precise metal hydride clusters, Cu<sub>24</sub>H<sub>6</sub>L<sub>12</sub>(PPh<sub>3</sub>)<sub>2</sub>Pz<sub>6</sub> (<b xmlns:bkstg="http://www.atypon.com/backstage-ns" xmlns:fn="http://www.w3.org/2005/xpath-functions" xmlns:pxje="java:com.atypon.frontend.services.impl.PassportXslJavaExtentions" xmlns:urlutil="java:com.atypon.literatum.customization.UrlUtil" xmlns:xlink="http://www.w3.org/1999/xlink"> <bold>Cu@Cu<sub>23</sub>H<sub>6</sub></bold></b>,) and Cu<sub>24-x</sub>Ag<sub>x</sub>H<sub>6</sub>L<sub>12</sub>(PPh<sub>3</sub>)<sub>2</sub>Pz<sub>6</sub> (0 > x > 1) (<b xmlns:bkstg="http://www.atypon.com/backstage-ns" xmlns:fn="http://www.w3.org/2005/xpath-functions" xmlns:pxje="java:com.atypon.frontend.services.impl.PassportXslJavaExtentions" xmlns:urlutil="java:com.atypon.literatum.customization.UrlUtil" xmlns:xlink="http://www.w3.org/1999/xlink"> <bold>Ag@Cu<sub>23</sub>H<sub>6</sub></bold></b>) (L= CH<sub>3</sub>OPhC≡C<sup>−</sup>, Pz = 3,5-(CF<sub>3</sub>)<sub>2</sub>-pyrazolate), containing M@Cu<sub>23</sub> (M=Cu/Ag) kernels with D<sub>3</sub>-symmetry. Single crystal X-ray diffraction results reveal that the DNA-like double-helical nanostructures driven by intrastrand and interstrand supramolecular interactions, including weak hydrogen bonds (i.e., C–H···F/O/C) and van der Waal’s interactions (i.e., C···F and F···F), are formed through the self-hierarchical assembly of<b xmlns:bkstg="http://www.atypon.com/backstage-ns" xmlns:fn="http://www.w3.org/2005/xpath-functions" xmlns:pxje="java:com.atypon.frontend.services.impl.PassportXslJavaExtentions" xmlns:urlutil="java:com.atypon.literatum.customization.UrlUtil" xmlns:xlink="http://www.w3.org/1999/xlink"> <bold> Cu@Cu<sub>23</sub>H<sub>6</sub></bold></b> and <b xmlns:bkstg="http://www.atypon.com/backstage-ns" xmlns:fn="http://www.w3.org/2005/xpath-functions" xmlns:pxje="java:com.atypon.frontend.services.impl.PassportXslJavaExtentions" xmlns:urlutil="java:com.atypon.literatum.customization.UrlUtil" xmlns:xlink="http://www.w3.org/1999/xlink"> <bold>Ag@Cu<sub>23</sub>H<sub>6</sub></bold></b>. In addition, <b xmlns:bkstg="http://www.atypon.com/backstage-ns" xmlns:fn="http://www.w3.org/2005/xpath-functions" xmlns:pxje="java:com.atypon.frontend.services.impl.PassportXslJavaExtentions" xmlns:urlutil="java:com.atypon.literatum.customization.UrlUtil" xmlns:xlink="http://www.w3.org/1999/xlink"> <bold>Cu@Cu<sub>23</sub>H<sub>6</sub></bold></b> is nonemissive. After doping with Ag, <b xmlns:bkstg="http://www.atypon.com/backstage-ns" xmlns:fn="http://www.w3.org/2005/xpath-functions" xmlns:pxje="java:com.atypon.frontend.services.impl.PassportXslJavaExtentions" xmlns:urlutil="java:com.atypon.literatum.customization.UrlUtil" xmlns:xlink="http://www.w3.org/1999/xlink"> <bold>Ag@Cu<sub>23</sub>H<sub>6</sub><
{"title":"Double-Helical Assembly of a Copper-Silver Hydride Cluster Exhibiting Thermally Activated Delayed Fluorescence","authors":"Hu Yang, Su-Kao Peng, Wenbin Chen, Dong Luo, Shibo Xi, Shuai Lu, Yong-Liang Huang, De-Bo Hao, Bincheng Cai, Heng Wang, Mo Xie, Ming-De Li, Xiaopeng Li, Guo-Hong Ning, Dan Li","doi":"10.31635/ccschem.024.202404213","DOIUrl":"https://doi.org/10.31635/ccschem.024.202404213","url":null,"abstract":"<p>The synthesis of helical nanostructures with advanced functions from atomically precise building blocks is attractive, but remains a significant challenge. In this work, we report two atomically precise metal hydride clusters, Cu<sub>24</sub>H<sub>6</sub>L<sub>12</sub>(PPh<sub>3</sub>)<sub>2</sub>Pz<sub>6</sub> (<b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\">\u0000<bold>Cu@Cu<sub>23</sub>H<sub>6</sub></bold></b>,) and Cu<sub>24-x</sub>Ag<sub>x</sub>H<sub>6</sub>L<sub>12</sub>(PPh<sub>3</sub>)<sub>2</sub>Pz<sub>6</sub> (0 > x > 1) (<b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\">\u0000<bold>Ag@Cu<sub>23</sub>H<sub>6</sub></bold></b>) (L= CH<sub>3</sub>OPhC≡C<sup>−</sup>, Pz = 3,5-(CF<sub>3</sub>)<sub>2</sub>-pyrazolate), containing M@Cu<sub>23</sub> (M=Cu/Ag) kernels with D<sub>3</sub>-symmetry. Single crystal X-ray diffraction results reveal that the DNA-like double-helical nanostructures driven by intrastrand and interstrand supramolecular interactions, including weak hydrogen bonds (i.e., C–H···F/O/C) and van der Waal’s interactions (i.e., C···F and F···F), are formed through the self-hierarchical assembly of<b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\">\u0000<bold> Cu@Cu<sub>23</sub>H<sub>6</sub></bold></b> and <b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\">\u0000<bold>Ag@Cu<sub>23</sub>H<sub>6</sub></bold></b>. In addition, <b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\">\u0000<bold>Cu@Cu<sub>23</sub>H<sub>6</sub></bold></b> is nonemissive. After doping with Ag, <b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\">\u0000<bold>Ag@Cu<sub>23</sub>H<sub>6</sub><","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"33 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142236297","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-16DOI: 10.31635/ccschem.024.202404675
CCS Chemistry, Ahead of Print.
CCS Chemistry, Ahead of Print.
{"title":"Heterogenization of a Dinuclear Cobalt Molecular Catalyst in Porous Polymers via Covalent Strategy for CO2 Photoreduction with Record CO Production Efficiency","authors":"","doi":"10.31635/ccschem.024.202404675","DOIUrl":"https://doi.org/10.31635/ccschem.024.202404675","url":null,"abstract":"CCS Chemistry, Ahead of Print.<br/>","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"11 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142235216","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-10DOI: 10.31635/ccschem.024.202404591
Jian-Guo Liu, Bo Liu, Ziyan Li, Ming-Hua Xu
Recent advances in transition metal-asymmetric carbene B–H insertion reactions provide a straightforward and powerful protocol to access chiral organoboron compounds. However, the related reaction involving linear alkyl carbenes has not been successfully developed. Apart from the difficulty of controlling the enantioselectivity, another major challenge is the high propensity of the alkyl metal carbene to undergo a β-hydride migration to form undesired alkenes. Herein, we report our development of an efficient alkyl carbene B–H insertion reaction using rhodium(I)/diene complexes as the catalysts. This simple catalytic system not only reduces the formation of alkene byproduct but also achieves high enantioselectivity of the carbene B–H insertion. This method facilitates easy asymmetric access to a wide variety of structurally diverse alkylboranes in high yields, and their further synthetic application and transformation have also been described. Mechanistic studies show that the β-hydride migration is less favorable than the carbene insertion pathway under the rhodium(I)/diene catalytic system and that the B–H bond insertion is the rate-limiting step.
{"title":"Rhodium(I)-Catalyzed Asymmetric Alkyl Carbene B–H Bond Insertion: Enantioselective Synthesis of Versatile Chiral Alkylboranes","authors":"Jian-Guo Liu, Bo Liu, Ziyan Li, Ming-Hua Xu","doi":"10.31635/ccschem.024.202404591","DOIUrl":"https://doi.org/10.31635/ccschem.024.202404591","url":null,"abstract":"<p>Recent advances in transition metal-asymmetric carbene B–H insertion reactions provide a straightforward and powerful protocol to access chiral organoboron compounds. However, the related reaction involving linear alkyl carbenes has not been successfully developed. Apart from the difficulty of controlling the enantioselectivity, another major challenge is the high propensity of the alkyl metal carbene to undergo a β-hydride migration to form undesired alkenes. Herein, we report our development of an efficient alkyl carbene B–H insertion reaction using rhodium(I)/diene complexes as the catalysts. This simple catalytic system not only reduces the formation of alkene byproduct but also achieves high enantioselectivity of the carbene B–H insertion. This method facilitates easy asymmetric access to a wide variety of structurally diverse alkylboranes in high yields, and their further synthetic application and transformation have also been described. Mechanistic studies show that the β-hydride migration is less favorable than the carbene insertion pathway under the rhodium(I)/diene catalytic system and that the B–H bond insertion is the rate-limiting step.</p>","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"83 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142166602","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-10DOI: 10.31635/ccschem.024.202404707
CCS Chemistry, Ahead of Print.
CCS Chemistry, Ahead of Print.
{"title":"Asymmetric Self-Assembled Monolayer as Hole Transport Layer Enables Binary Organic Solar Cells Based on PM6: Y6 with Over 19% Efficiency","authors":"","doi":"10.31635/ccschem.024.202404707","DOIUrl":"https://doi.org/10.31635/ccschem.024.202404707","url":null,"abstract":"CCS Chemistry, Ahead of Print.<br/>","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"104 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142166600","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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