70887-29-5Relevant articles and documents
One-Pot Deoxygenation and Substitution of Alcohols Mediated by Sulfuryl Fluoride
Epifanov, Maxim,Mo, Jia Yi,Dubois, Rudy,Yu, Hao,Sammis, Glenn M.
, p. 3768 - 3777 (2021/03/01)
Sulfuryl fluoride is a valuable reagent for the one-pot activation and derivatization of aliphatic alcohols, but the highly reactive alkyl fluorosulfate intermediates limit both the types of reactions that can be accessed as well as the scope. Herein, we report the SO2F2-mediated alcohol substitution and deoxygenation method that relies on the conversion of fluorosulfates to alkyl halide intermediates. This strategy allows the expansion of SO2F2-mediated one-pot processes to include radical reactions, where the alkyl halides can also be exploited in the one-pot deoxygenation of primary alcohols under mild conditions (52-95% yield). This strategy can also enhance the scope of substitutions to nucleophiles that are previously incompatible with one-pot SO2F2-mediated alcohol activation and enables substitution of primary and secondary alcohols in 54-95% yield. Chiral secondary alcohols undergo a highly stereospecific (90-98% ee) double nucleophilic displacement with an overall retention of configuration.
Iminophosphorane-mediated regioselective umpolung alkylation reaction of α-iminoesters
Kukita, Mayu,Mino, Takashi,Omori, Kazuki,Sakamoto, Masami,Yoshida, Yasushi
, p. 4551 - 4564 (2021/05/31)
Umpolung reactions of imines, especially the asymmetric reactions, have been extensively studied as they provide access to important chiral amines in an efficient manner. The reactions studied range from simple Michael reactions to several kinds of other reactions such as the aza-benzoin reaction, aza-Stetter reaction, addition with MBH carbonate, and Ir-catalysed allylation. Herein, we report the first umpolung alkylation reaction of α-iminoesters with alkyl halides mediated by iminophosphorane as an organic superbase. The desired products were obtained in up to 82% yield with almost perfect regioselectivities. The key to the regioselectivity of this reaction was the use of 4-trifluoromethyl benzyl imines as a substrate. The products were successfully derivatised into the more functionalised molecules in good yields.
Method for efficiently preparing benzyl iodide and derivatives thereof
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Paragraph 0035-0037, (2020/07/12)
The invention discloses a method for efficiently preparing benzyl iodide and derivatives thereof. The benzyl iodide and the derivatives thereof are prepared by using a benzaldehyde compound as the initial raw material through complex reaction, main reaction and post-reaction. The method specifically includes: placing rhodium and phosphine ligand into a reaction container, adding an organic solvent, stirring for complexing to obtain a reaction system a, adding iodine, stirring under room temperature, adding the initial material benzaldehyde compound to continuously perform stirring reaction toobtain reaction liquid b, transferring into a high-pressure reaction kettle, performing gas replacement, filling hydrogen, keeping positive pressure, performing reaction under room temperature for 4-48 hours to obtain reaction liquid c, and performing vacuum concentration and column chromatography purification to obtain the target benzyl iodide and the derivatives thereof. The method is cheap in used substrate, simple to operate, good in reaction operation safety, environmentally friendly, high in yield, high in the purity of the benzyl iodide and the derivatives thereof, easy to achieve large-scale production and capable of achieving industrial production to satisfy social medical requirements.
