Ondřej Moždiak, Tomáš Bíza, Lukáš Střižík, Zdeňka Růžičková, Milan Erben, Libor Dostál, Emanuel Hupf, Roman Jambor
{"title":"从Sn（II）阳离子催化的硼氢化反应到光致发光硼酯","authors":"Ondřej Moždiak, Tomáš Bíza, Lukáš Střižík, Zdeňka Růžičková, Milan Erben, Libor Dostál, Emanuel Hupf, Roman Jambor","doi":"10.1002/cctc.202500462","DOIUrl":null,"url":null,"abstract":"<p>The <i>N</i>-coordinated Sn(II) cations [{(2,6-<i>i</i>Pr<sub>2</sub>-C<sub>6</sub>H<sub>3</sub>)-N = C(Me)-(6-MeO)-C<sub>5</sub>H<sub>3</sub>N}SnCl](SnCl<sub>3</sub>) (<b>1</b>), [{(2,6-<i>i</i>Pr<sub>2</sub>-C<sub>6</sub>H<sub>3</sub>)-N = C(Me)-(6-P(O)(O<i>i</i>Pr)<sub>2</sub>)-C<sub>5</sub>H<sub>3</sub>N}SnCl](SnCl<sub>3</sub>) (<b>2</b>), and [{(1,2-(C<sub>5</sub>H<sub>4</sub>N-2-CH = N)<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>)}SnCl](SnCl<sub>3</sub>) (<b>3</b>) were prepared and used as catalysts in the hydroboration of ketones and aldehydes. Mechanistic and kinetic studies provide evidence that these electrophiles interact with the C═O bond of the substrates and indicate a pseudo-first-order reaction with a rate constant of <i>k</i> = 70.2 h<sup>−1</sup> using 2 mol% of <b>1. 1</b> could effectively be used as a catalyst in the hydroboration of a broad range of substrates including, substituted benzaldehydes, heterocyclic carbaldehydes, and aliphatic aldehydes, as well as ketones. Finally, <b>1</b> was used in large-scale hydroboration reactions of pyridine-substituted carbaldehydes to prepare the respective pyridine-substituted boronic esters [2-(PinBOCH<sub>2</sub>)-C<sub>5</sub>H<sub>4</sub>N] (<b>4</b>), [2-(PinBOCH<sub>2</sub>)-4-(MeO)-C<sub>5</sub>H<sub>3</sub>N] (<b>5</b>), [2-(PinBOCH<sub>2</sub>)-6-(MeO)-C<sub>5</sub>H<sub>3</sub>N] (<b>6</b>), [2-(PinBOCH<sub>2</sub>)-6-Br-C<sub>5</sub>H<sub>3</sub>N] (<b>7</b>), [2-(PinBOCH<sub>2</sub>)-5-Br-C<sub>5</sub>H<sub>3</sub>N] (<b>8</b>), [3-(PinBOCH<sub>2</sub>)-C<sub>5</sub>H<sub>4</sub>N] (<b>9</b>), and borinate [2-[(BBN)OCH<sub>2</sub>]-4-(MeO)-C<sub>5</sub>H<sub>3</sub>N] (<b>10</b>), which were characterized by NMR spectroscopy, single-crystal X-ray structure analysis, and an analysis of their photoluminescence.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 18","pages":""},"PeriodicalIF":3.9000,"publicationDate":"2025-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.202500462","citationCount":"0","resultStr":"{\"title\":\"From Hydroborations Catalyzed by Sn(II) Cations to Photoluminescent Boronic Esters\",\"authors\":\"Ondřej Moždiak, Tomáš Bíza, Lukáš Střižík, Zdeňka Růžičková, Milan Erben, Libor Dostál, Emanuel Hupf, Roman Jambor\",\"doi\":\"10.1002/cctc.202500462\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>The <i>N</i>-coordinated Sn(II) cations [{(2,6-<i>i</i>Pr<sub>2</sub>-C<sub>6</sub>H<sub>3</sub>)-N = C(Me)-(6-MeO)-C<sub>5</sub>H<sub>3</sub>N}SnCl](SnCl<sub>3</sub>) (<b>1</b>), [{(2,6-<i>i</i>Pr<sub>2</sub>-C<sub>6</sub>H<sub>3</sub>)-N = C(Me)-(6-P(O)(O<i>i</i>Pr)<sub>2</sub>)-C<sub>5</sub>H<sub>3</sub>N}SnCl](SnCl<sub>3</sub>) (<b>2</b>), and [{(1,2-(C<sub>5</sub>H<sub>4</sub>N-2-CH = N)<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>)}SnCl](SnCl<sub>3</sub>) (<b>3</b>) were prepared and used as catalysts in the hydroboration of ketones and aldehydes. Mechanistic and kinetic studies provide evidence that these electrophiles interact with the C═O bond of the substrates and indicate a pseudo-first-order reaction with a rate constant of <i>k</i> = 70.2 h<sup>−1</sup> using 2 mol% of <b>1. 1</b> could effectively be used as a catalyst in the hydroboration of a broad range of substrates including, substituted benzaldehydes, heterocyclic carbaldehydes, and aliphatic aldehydes, as well as ketones. Finally, <b>1</b> was used in large-scale hydroboration reactions of pyridine-substituted carbaldehydes to prepare the respective pyridine-substituted boronic esters [2-(PinBOCH<sub>2</sub>)-C<sub>5</sub>H<sub>4</sub>N] (<b>4</b>), [2-(PinBOCH<sub>2</sub>)-4-(MeO)-C<sub>5</sub>H<sub>3</sub>N] (<b>5</b>), [2-(PinBOCH<sub>2</sub>)-6-(MeO)-C<sub>5</sub>H<sub>3</sub>N] (<b>6</b>), [2-(PinBOCH<sub>2</sub>)-6-Br-C<sub>5</sub>H<sub>3</sub>N] (<b>7</b>), [2-(PinBOCH<sub>2</sub>)-5-Br-C<sub>5</sub>H<sub>3</sub>N] (<b>8</b>), [3-(PinBOCH<sub>2</sub>)-C<sub>5</sub>H<sub>4</sub>N] (<b>9</b>), and borinate [2-[(BBN)OCH<sub>2</sub>]-4-(MeO)-C<sub>5</sub>H<sub>3</sub>N] (<b>10</b>), which were characterized by NMR spectroscopy, single-crystal X-ray structure analysis, and an analysis of their photoluminescence.</p>\",\"PeriodicalId\":141,\"journal\":{\"name\":\"ChemCatChem\",\"volume\":\"17 18\",\"pages\":\"\"},\"PeriodicalIF\":3.9000,\"publicationDate\":\"2025-07-15\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.202500462\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ChemCatChem\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cctc.202500462\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ChemCatChem","FirstCategoryId":"92","ListUrlMain":"https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cctc.202500462","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
From Hydroborations Catalyzed by Sn(II) Cations to Photoluminescent Boronic Esters
The N-coordinated Sn(II) cations [{(2,6-iPr2-C6H3)-N = C(Me)-(6-MeO)-C5H3N}SnCl](SnCl3) (1), [{(2,6-iPr2-C6H3)-N = C(Me)-(6-P(O)(OiPr)2)-C5H3N}SnCl](SnCl3) (2), and [{(1,2-(C5H4N-2-CH = N)2CH2CH2)}SnCl](SnCl3) (3) were prepared and used as catalysts in the hydroboration of ketones and aldehydes. Mechanistic and kinetic studies provide evidence that these electrophiles interact with the C═O bond of the substrates and indicate a pseudo-first-order reaction with a rate constant of k = 70.2 h−1 using 2 mol% of 1. 1 could effectively be used as a catalyst in the hydroboration of a broad range of substrates including, substituted benzaldehydes, heterocyclic carbaldehydes, and aliphatic aldehydes, as well as ketones. Finally, 1 was used in large-scale hydroboration reactions of pyridine-substituted carbaldehydes to prepare the respective pyridine-substituted boronic esters [2-(PinBOCH2)-C5H4N] (4), [2-(PinBOCH2)-4-(MeO)-C5H3N] (5), [2-(PinBOCH2)-6-(MeO)-C5H3N] (6), [2-(PinBOCH2)-6-Br-C5H3N] (7), [2-(PinBOCH2)-5-Br-C5H3N] (8), [3-(PinBOCH2)-C5H4N] (9), and borinate [2-[(BBN)OCH2]-4-(MeO)-C5H3N] (10), which were characterized by NMR spectroscopy, single-crystal X-ray structure analysis, and an analysis of their photoluminescence.
期刊介绍：
With an impact factor of 4.495 (2018), ChemCatChem is one of the premier journals in the field of catalysis. The journal provides primary research papers and critical secondary information on heterogeneous, homogeneous and bio- and nanocatalysis. The journal is well placed to strengthen cross-communication within between these communities. Its authors and readers come from academia, the chemical industry, and government laboratories across the world. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies, and is supported by the German Catalysis Society.
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