Pd/PVP 与 CO2 和二甲胺硼烷催化胺和硝基烯烃甲酰化为 N-甲酰胺：二氧化碳对形成氮氧茚的影响。

IF 3.8 3区化学 Q2 CHEMISTRY, PHYSICAL

ChemCatChem Pub Date : 2024-08-30 DOI:10.1002/cctc.202401260

Anna Skarżyńska, Wojciech Gil, Anna Trzeciak

{"title":"Pd/PVP 与 CO2 和二甲胺硼烷催化胺和硝基烯烃甲酰化为 N-甲酰胺：二氧化碳对形成氮氧茚的影响。","authors":"Anna Skarżyńska, Wojciech Gil, Anna Trzeciak","doi":"10.1002/cctc.202401260","DOIUrl":null,"url":null,"abstract":"The reactivity of dimethylamine borane (DMAB) towards amines and nitroarenes was investigated in the presence of the CO2 and Pd/PVP (PVP = polyvinylpyrrolidone) nanocatalyst. The formation of borane formate, Me2NH.BH2(OCHO), by the insertion of CO2 into the B‐H bond was evidenced by NMR. The reaction of DMAB with CO2 also produced a second product, DMF, formed via self‐formylation. In the presence of aromatic or aliphatic amines corresponding N‐formamides were formed efficiently. Under the same conditions nitroarenes were hydrogenated to anilines or to azoxyarenes in the absence of CO2. In both reactions very high TOF values, up to 30 min‐1, were obtained. Applying a higher excess of DMAB enabled the transformation of nitroarenes to N‐formamides. The Pd/PVP catalyst was used in 7 consecutive cycles of N‐methylaniline formylation with excellent selectivity and a total TON equal to 4700.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"52 1","pages":""},"PeriodicalIF":3.8000,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Pd/PVP‐Catalyzed Formylation of Amines and Nitroarenes to N‐formamides with CO2 and Dimethylamine Borane: The Influence of CO2 on the Formation of Azoxyarenes.\",\"authors\":\"Anna Skarżyńska, Wojciech Gil, Anna Trzeciak\",\"doi\":\"10.1002/cctc.202401260\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"The reactivity of dimethylamine borane (DMAB) towards amines and nitroarenes was investigated in the presence of the CO2 and Pd/PVP (PVP = polyvinylpyrrolidone) nanocatalyst. The formation of borane formate, Me2NH.BH2(OCHO), by the insertion of CO2 into the B‐H bond was evidenced by NMR. The reaction of DMAB with CO2 also produced a second product, DMF, formed via self‐formylation. In the presence of aromatic or aliphatic amines corresponding N‐formamides were formed efficiently. Under the same conditions nitroarenes were hydrogenated to anilines or to azoxyarenes in the absence of CO2. In both reactions very high TOF values, up to 30 min‐1, were obtained. Applying a higher excess of DMAB enabled the transformation of nitroarenes to N‐formamides. The Pd/PVP catalyst was used in 7 consecutive cycles of N‐methylaniline formylation with excellent selectivity and a total TON equal to 4700.\",\"PeriodicalId\":141,\"journal\":{\"name\":\"ChemCatChem\",\"volume\":\"52 1\",\"pages\":\"\"},\"PeriodicalIF\":3.8000,\"publicationDate\":\"2024-08-30\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ChemCatChem\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1002/cctc.202401260\",\"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://doi.org/10.1002/cctc.202401260","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}

引用次数: 0

摘要

在二氧化碳和 Pd/PVP（PVP=聚乙烯吡咯烷酮）纳米催化剂存在下，研究了二甲基胺硼烷（DMAB）与胺和硝基烯烃的反应活性。核磁共振证明了 CO2 插入 B-H 键后形成的硼烷甲酸酯 Me2NH.BH2(OCHO)。DMAB 与 CO2 反应还产生了第二种产物，即通过自甲酰化形成的 DMF。在芳香族或脂肪族胺的存在下，相应的 N-甲酰胺会有效地生成。在相同条件下，硝基烯烃在没有 CO2 的情况下氢化成苯胺或偶氮烯烃。在这两个反应中都获得了非常高的 TOF 值，最高可达 30 min-1。使用过量的 DMAB 可以将硝基烯烃转化为 N-甲酰胺。Pd/PVP 催化剂连续 7 次用于 N-甲基苯胺甲酰化反应，具有极佳的选择性，总吨位为 4700。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

查看原文本刊更多论文

Pd/PVP‐Catalyzed Formylation of Amines and Nitroarenes to N‐formamides with CO2 and Dimethylamine Borane: The Influence of CO2 on the Formation of Azoxyarenes.

The reactivity of dimethylamine borane (DMAB) towards amines and nitroarenes was investigated in the presence of the CO2 and Pd/PVP (PVP = polyvinylpyrrolidone) nanocatalyst. The formation of borane formate, Me2NH.BH2(OCHO), by the insertion of CO2 into the B‐H bond was evidenced by NMR. The reaction of DMAB with CO2 also produced a second product, DMF, formed via self‐formylation. In the presence of aromatic or aliphatic amines corresponding N‐formamides were formed efficiently. Under the same conditions nitroarenes were hydrogenated to anilines or to azoxyarenes in the absence of CO2. In both reactions very high TOF values, up to 30 min‐1, were obtained. Applying a higher excess of DMAB enabled the transformation of nitroarenes to N‐formamides. The Pd/PVP catalyst was used in 7 consecutive cycles of N‐methylaniline formylation with excellent selectivity and a total TON equal to 4700.

求助全文

通过发布文献求助，成功后即可免费获取论文全文。去求助

来源期刊

ChemCatChem 化学-物理化学

CiteScore

8.10

自引率

4.40%

发文量

511

审稿时长

1.3 months

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.