2928-17-8Relevant academic research and scientific papers
Synergistic Catalysis for the Umpolung Trifluoromethylthiolation of Tertiary Ethers
Xu, Wentao,Ma, Junyang,Yuan, Xiang-Ai,Dai, Jie,Xie, Jin,Zhu, Chengjian
supporting information, p. 10357 - 10361 (2018/08/06)
The first transition-metal-free, site-specific umpolung trifluoromethylthiolation of tertiary alkyl ethers has been developed, achieving the challenging tertiary C(sp3)–SCF3 coupling under redox-neutral conditions. The synergism of organophotocatalyst 4CzIPN and BINOL-based phosphorothiols can site-selectively cleave tertiary sp3 C(sp3)–O ether bonds in complex molecules initiated by a polarity-matching hydrogen-atom-transfer (HAT) event. The incorporation of several competing benzylic and methine C(sp3)?H bonds in alkyl ethers has little influence on the regioselectivity. Selective difluoromethylthiolation of C?O bonds has also been achieved. This represents not only an important step forward in trifluoromethylthiolation but also a promising means for site-selective C?O bond functionalization of unsymmetrical tertiary alkyl ethers.
1 — (4 — Fluorophenyl) — 2 — methyl — 2 — propylamine synthetic method
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Paragraph 0027-0030, (2018/04/01)
The invention relates to the synthesis of organic substances, in particular to a synthetic method of 1-(4-fluorophenyl)-2-methyl-2-propylamine, comprising the following steps of: firstly, synthesizing 1,1-dimethyl parafluorobenzoic alcohol: adding magnesium powder dried at 95 DEG C by heating into an organic solution of parafluorobenzoic chloride to react, then dropping acetone to react, and then adding 5-20 percent of diluted hydrochloric acid solution, depositing a lemon-yellow organic phase and distilling off the organic solution by a rotary atmometer; secondly, synthesizing parafluoro acylamide: adding acetonitrile and acid liquor which are used as raw materials into the 1,1-dimethyl parafluorobenzoic alcohol to react, then distilling off the acetonitrile, adding a reaction liquid into water, then adding sodium hydroxide for neutralizing until the pH value reaches 6-7, separating out white solid particles, filtering and washing; and thirdly, synthesizing the 1-(4-fluorophenyl)-2-methyl-2-propylamine: adding the parafluoro acylamide and potassium hydroxide solution into a high pressure kettle, replacing with nitrogen, and then depositing a lemon-yellow oil layer to obtain a crude product. The invention has reasonable synthesis route, mild reaction, easy operation, low cost of raw materials, high product yield and high purity.
Pd(II)-catalyzed hydroxyl-directed C-H olefination enabled by monoprotected amino acid ligands
Lu, Yi,Wang, Dong-Hui,Engle, Keary M.,Yu, Jin-Quan
supporting information; experimental part, p. 5916 - 5921 (2010/07/05)
A novel Pd(II)-catalyzed ortho-C-H olefination protocol has been developed using spatially remote, unprotected tertiary, secondary, and primary alcohols as the directing groups. Mono-N-protected amino acid ligands were found to promote the reaction, and an array of olefin coupling partners could be used. When electron-deficient alkenes were used, the resulting olefinated intermediates underwent subsequent Pd(II)-catalyzed oxidative intramolecular cyclization to give the corresponding pyran products, which could be converted into ortho-alkylated alcohols under hydrogenolysis conditions. The mechanistic details of the oxidative cyclization step are discussed and situated in the context of the overall catalytic cycle.
