A study of the reaction of perfluoroalkyl Grignard reagents with phosphoryl chloride and phenylphosphonic dichloride
作者:Adil I. Hosein、Andrew J. M. Caffyn
DOI:10.1039/c2dt31371e
日期:——
Perfluoroalkyl Grignard reagents react with phosphoryl halides at −78 °C to room temperature to selectively produce bis(perfluoroalkyl)phosphonyl halides, which after aqueous work up, give bis(perfluoroalkyl)phosphinic acids in high overall yields. Reaction of perfluoroalkyl Grignards with phenylphosphonic dichloride gives high yields of bis(perfluoroalkyl)phenyl phosphine oxides which are readily
Chemo‐ and Regioselective Ring Construction Driven by Visible‐Light Photoredox Catalysis: an Access to Fluoroalkylated Oxazolidines Featuring an All‐Substituted Carbon Stereocenter
ether, fluoroalkyl halide, and chiral amino alcohol in a single reaction vessel, which provides an efficient strategy for expanding the pool of pharmaceutically important heterocycles featuring an all‐substituted carbon stereocenter. This process proceeds efficiently in a chemo‐, regio‐, and stereoselective fashion under mild reaction conditions at room temperature and exhibits broad functional group
Synthesis of Polycyclic Furan and Chromene Derivatives
<i>via</i>
Cascade Reactions Enabled by Cleavage of Multiple C(
<i>sp</i>
<sup>3</sup>
)−F Bonds
and unreactive C−Fbond makes polyfluorocarbons extremely long‐lived and potentially toxic. A successive selective and controllable C(sp3)−F functionalization of polyfluoroalkylated ketones with S‐ and O‐nucleophiles to enable efficient synthesis of pharmaceutically important fluorine‐ and sulfur‐containing polycyclic furan and chromene derivatives under transition metal‐free conditions is demonstrated
牢固且无反应的C-F键使聚碳氟化合物寿命极长,并且可能具有毒性。本文展示了具有S和O亲核试剂的多氟烷基化酮的连续选择性和可控C(sp 3)-F功能化,可在无过渡金属的条件下有效合成重要的药学上重要的含氟和硫的多环呋喃和亚甲基苯衍生物。 。C-S / C-O偶联,芳构化和环化级联的组合有助于形成精确的4/5 C(sp 3)-F键在全氟烷基链的两个不同位点裂解。通过详细的机理研究,确定了反应性醌型中间体的形成以及使用TBAB(溴化四丁基铵)作为添加剂和Cs 2 CO 3作为碱的必要性。
Perfluoro-n-heptylcopper(I) has been treated with 1-hexyne and 1-decyne to give 1-perfluoro-n-heptyl-1-hexene and-1-decene respectively. Reaction of the copper derivative with propargyl bromide and 3-hydroxy-3-methyl-1-butyne yielded 1-perfluoro-n-heptyl-1,2-propadiene and 1-perfluoroheptyl-3-methyl-1,2-butadiene respectively. Reactions of perfluoroalkylcopper(1) compounds CF3(CF2)nCu(n = 4—8) with