Jérémy Willot, Sana Fatima, Carine Duhayon, Noël Lugan, Yves Canac, Dmitry A. Valyaev
{"title":"锰介导的 NHC-膦配体前体合成","authors":"Jérémy Willot, Sana Fatima, Carine Duhayon, Noël Lugan, Yves Canac, Dmitry A. Valyaev","doi":"10.1002/hlca.202400009","DOIUrl":null,"url":null,"abstract":"<p>Alkylation of <i>N</i>-substituted imidazoles ImR’ (R’=2,4,6-trimethylphenyl, 2,6-diisopropylphenyl, 1-adamantyl) with Mn(I) methylenephosphonium complexes [Cp(CO)<sub>2</sub>Mn(η<sup>2</sup>-<i>P,C</i>-R<sub>2</sub>P=C(H)Ph)](BF<sub>4</sub>) (PR<sub>2</sub>=PPh<sub>2</sub>, PCy<sub>2</sub>, <i>trans</i>-P<span>C(H)PhCH<sub>2</sub>CH<sub>2</sub>C</span> (H)Ph) followed by photochemical demetallation afforded a series of bidentate NHC-phosphine ligand precursors [R<sub>2</sub>PC(H)PhImR’](BF<sub>4</sub>) in moderate to good yield. The same strategy was successfully applied to <i>N</i>-functionalized imidazoles ImL (L=2-pyridyl, CH<sub>2</sub>SMe, CH<sub>2</sub>ImMe) to afford selectively NHC core pincer pre-ligands featuring phosphine/thioether, phosphine/NHC and phosphine/pyridine side arms. For PCy<sub>2</sub> derivatives, free NHCs in both bidentate and pincer series generated by deprotonation of the corresponding cationic precursors were shown to be persistent at room temperature.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"107 4","pages":""},"PeriodicalIF":1.5000,"publicationDate":"2024-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Manganese-Mediated Synthesis of NHC-Phosphine Ligand Precursors\",\"authors\":\"Jérémy Willot, Sana Fatima, Carine Duhayon, Noël Lugan, Yves Canac, Dmitry A. Valyaev\",\"doi\":\"10.1002/hlca.202400009\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Alkylation of <i>N</i>-substituted imidazoles ImR’ (R’=2,4,6-trimethylphenyl, 2,6-diisopropylphenyl, 1-adamantyl) with Mn(I) methylenephosphonium complexes [Cp(CO)<sub>2</sub>Mn(η<sup>2</sup>-<i>P,C</i>-R<sub>2</sub>P=C(H)Ph)](BF<sub>4</sub>) (PR<sub>2</sub>=PPh<sub>2</sub>, PCy<sub>2</sub>, <i>trans</i>-P<span>C(H)PhCH<sub>2</sub>CH<sub>2</sub>C</span> (H)Ph) followed by photochemical demetallation afforded a series of bidentate NHC-phosphine ligand precursors [R<sub>2</sub>PC(H)PhImR’](BF<sub>4</sub>) in moderate to good yield. The same strategy was successfully applied to <i>N</i>-functionalized imidazoles ImL (L=2-pyridyl, CH<sub>2</sub>SMe, CH<sub>2</sub>ImMe) to afford selectively NHC core pincer pre-ligands featuring phosphine/thioether, phosphine/NHC and phosphine/pyridine side arms. For PCy<sub>2</sub> derivatives, free NHCs in both bidentate and pincer series generated by deprotonation of the corresponding cationic precursors were shown to be persistent at room temperature.</p>\",\"PeriodicalId\":12842,\"journal\":{\"name\":\"Helvetica Chimica Acta\",\"volume\":\"107 4\",\"pages\":\"\"},\"PeriodicalIF\":1.5000,\"publicationDate\":\"2024-03-05\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Helvetica Chimica Acta\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/hlca.202400009\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Helvetica Chimica Acta","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/hlca.202400009","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Manganese-Mediated Synthesis of NHC-Phosphine Ligand Precursors
Alkylation of N-substituted imidazoles ImR’ (R’=2,4,6-trimethylphenyl, 2,6-diisopropylphenyl, 1-adamantyl) with Mn(I) methylenephosphonium complexes [Cp(CO)2Mn(η2-P,C-R2P=C(H)Ph)](BF4) (PR2=PPh2, PCy2, trans-PC(H)PhCH2CH2C (H)Ph) followed by photochemical demetallation afforded a series of bidentate NHC-phosphine ligand precursors [R2PC(H)PhImR’](BF4) in moderate to good yield. The same strategy was successfully applied to N-functionalized imidazoles ImL (L=2-pyridyl, CH2SMe, CH2ImMe) to afford selectively NHC core pincer pre-ligands featuring phosphine/thioether, phosphine/NHC and phosphine/pyridine side arms. For PCy2 derivatives, free NHCs in both bidentate and pincer series generated by deprotonation of the corresponding cationic precursors were shown to be persistent at room temperature.
期刊介绍：
Helvetica Chimica Acta, founded by the Swiss Chemical Society in 1917, is a monthly multidisciplinary journal dedicated to the dissemination of knowledge in all disciplines of chemistry (organic, inorganic, physical, technical, theoretical and analytical chemistry) as well as research at the interface with other sciences, where molecular aspects are key to the findings. Helvetica Chimica Acta is committed to the publication of original, high quality papers at the frontier of scientific research. All contributions will be peer reviewed with the highest possible standards and published within 3 months of receipt, with no restriction on the length of the papers and in full color.
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