Manganese-Mediated Synthesis of NHC-Phosphine Ligand Precursors

IF 1.5 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Helvetica Chimica Acta Pub Date : 2024-03-05 DOI:10.1002/hlca.202400009
Jérémy Willot, Sana Fatima, Carine Duhayon, Noël Lugan, Yves Canac, Dmitry A. Valyaev
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Abstract

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.

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锰介导的 NHC-膦配体前体合成
N-取代咪唑 ImR'(R'=2,4,6-三甲基苯基、2,6-二异丙基苯基、1-金刚烷基)与亚甲基膦锰(I)配合物[Cp(CO)2Mn(η2-P,C-R2P=C(H)Ph)](BF4)(PR2=PPh2、PCy2、反式-PC(H)PhCH2CH2C(H)Ph)),然后进行光化学去金属化,得到了一系列双齿 NHC-膦配体前体[R2PC(H)PhImR'](BF4),收率中等至良好。同样的策略也成功地应用于 N-官能化咪唑 ImL(L = 2-吡啶基、CH2SMe、CH2ImMe),从而获得了具有膦/硫醚、膦/NHC 和膦/吡啶侧臂的选择性 NHC 核心钳形前配体。对于 PCy2 衍生物,通过相应阳离子前体的去质子化作用生成的双叉和钳形系列的游离 NHC 在室温下具有持久性。
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来源期刊
Helvetica Chimica Acta
Helvetica Chimica Acta 化学-化学综合
CiteScore
3.00
自引率
0.00%
发文量
60
审稿时长
2.3 months
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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Cover Picture: (Helv. Chim. Acta 9/2024) Cover Picture: (Helv. Chim. Acta 8/2024) Micelle Enabled Buchwald-Hartwig Amination in Water with the Bening by Design Surfactant TPGS-750-M for the Synthesis of the JAK Inhibitor 4-((2-Chlorophenyl)amino)-6-((6-methylpyridin-2-yl)amino)nicotinamide A Telescopic, Scalable and Industrially Feasible Method for the Synthesis of Antidepressant Drug, Moclobemide Cover Picture: (Helv. Chim. Acta 7/2024)
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