3376-23-6Relevant articles and documents
Regio- and stereoselective synthesis of novel isoxazolidine heterocycles by 1,3-dipolar cycloaddition between C-phenyl- N -methylnitrone and substituted alkenes. Experimental and DFT investigation of selectivity and mechanism
Hellel, Djamila,Chafaa, Fouad,Khorief Nacereddine, Abdelmalek,Djerourou, Abdelhafid,Vrancken, Emmanuel
, p. 30128 - 30141 (2017)
A series of isoxazolidine heterocycles was synthesized through the 1,3-dipolar cycloaddition (13DC) reaction of C-phenyl-N-methylnitrone with different substituted alkenes. The structures and stereochemistry of the cycloadducts were determined by spectroscopic methods. These 13DC reactions are characterized by complete regioselectivity and high stereoselectivity. The molecular mechanism, reactivity and selectivity of these 13DC reactions have been investigated by means of transition state theory and reactivity indices derived from conceptual DFT using DFT methods at the B3LYP/6-31G(d,p) level of theory. The obtained results indicate that these cycloaddition reactions take place through a one-step synchronous mechanism with a non-polar mechanism and high activation energies. The theoretical results are in agreement with the experimental findings.
Regio- and Enantioselective (3+3) Cycloaddition of Nitrones with 2-Indolylmethanols Enabled by Cooperative Organocatalysis
Li, Tian-Zhen,Liu, Si-Jia,Sun, Yu-Wen,Deng, Shuang,Tan, Wei,Jiao, Yinchun,Zhang, Yu-Chen,Shi, Feng
supporting information, p. 2355 - 2363 (2020/12/09)
The regio- and enantioselective (3+3) cycloaddition of nitrones with 2-indolylmethanols was accomplished by the cooperative catalysis of hexafluoroisopropanol (HFIP) and chiral phosphoric acid (CPA). Using this approach, a series of indole-fused six-membered heterocycles were synthesized in high yields (up to 98 %), with excellent enantioselectivities (up to 96 % ee) and exclusive regiospecificity. This approach enabled not only the first organocatalytic asymmetric (3+3) cycloaddition of nitrones but also the first C3-nucleophilic asymmetric (3+3) cycloaddition of 2-indolylmethanols. More importantly, theoretical calculations elucidated the role of the cocatalyst HFIP in helping CPA control the reactivity and enantioselectivity of the reaction, demonstrating a new mode of cooperative catalysis.
Nucleophilic Addition to Nitrones Using a Flow Microreactor
Arakawa, Yukihiro,Imada, Yasushi,Minagawa, Keiji,Okamoto, Takuma,Ueta, Shun
supporting information, p. 866 - 870 (2020/05/28)
Nucleophilic addition reactions of soft carbon nucleophiles to nitrones in a flow microreactor are reported for the first time. Under microflow conditions at 30 to 0 °C, a range of nitrones can be efficiently transformed into the corresponding oxyiminium ions by reaction with either acyl halides or trialkylsilyl triflates. These can subsequently undergo the addition of nucleophiles including allyltributylstannane, ketene methyl tert-butyldimethylsilyl acetal, and N-silyl ketene imines to afford the corresponding adducts in high yields; such reactions at a similar temperature under batch conditions resulted in lower yields because of undesired side reactions.