22234-62-4Relevant academic research and scientific papers
Continuous Platform to Generate Nitroalkanes On-Demand (in Situ) Using Peracetic Acid-Mediated Oxidation in a PFA Pipes-in-Series Reactor
Tsukanov, Sergey V.,Johnson, Martin D.,May, Scott A.,Kolis, Stanley P.,Yates, Matthew H.,Johnston, Jeffrey N.
, p. 971 - 977 (2018/08/28)
The synthetic utility of the aza-Henry reaction can be diminished on scale by potential hazards associated with the use of peracid to prepare nitroalkane substrates and the nitroalkanes themselves. In response, a continuous and scalable chemistry platform to prepare aliphatic nitroalkanes on-demand using the oxidation of oximes with peracetic acid and direct reaction of the nitroalkane intermediate in an aza-Henry reaction is reported. A uniquely designed pipes-in-series plug-flow tube reactor addresses a range of process challenges, including stability and safe handling of peroxides and nitroalkanes. The subsequent continuous extraction generates a solution of purified nitroalkane, which can be directly used in the following enantioselective aza-Henry chemistry to furnish valuable chiral diamine precursors with high selectivity, thus completely avoiding isolation of the potentially unsafe low-molecular-weight nitroalkane intermediate. A continuous campaign (16 h) established that these conditions were effective in processing 100 g of the oxime and furnishing 1.4 L of nitroalkane solution.
Metal-Catalyzed Synthesis of Functionalized 1,2,4-Oxadiazoles from Silyl Nitronates and Nitriles
Nikodemiak, Paul,Koert, Ulrich
supporting information, p. 1708 - 1716 (2017/05/22)
The metal-catalyzed cycloaddition of silyl nitronates and nitriles leading to 1,2,4-oxadiazoles is described. Silver(I) triflate (AgOTf) and and ytterbium(III) triflate [Yb(OTf)3] are suitable catalysts. A variety of functional groups is tolerated in the nitrile. The reaction works well for alkenyl and aryl silyl nitronates while the use of alkyl silyl nitronates is less efficient. Mechanistic studies are in favour of an elimination of tert-butyl(dimethyl)silanol (TBSOH) after the cycloaddition step. The new approach has also been applied for the synthesis of the drug ataluren. (Figure presented.).
Minimizing the amount of nitromethane in palladium-catalyzed cross-coupling with aryl halides
Walvoord, Ryan R.,Kozlowski, Marisa C.
, p. 8859 - 8864 (2013/09/24)
A method for the formation of arylnitromethanes is described that employs readily available aryl halides or triflates and small amounts of nitromethane in a dioxane solvent, thereby reducing the hazards associated with this reagent. Specifically, 2-10 equiv (1-5% v/v) of nitromethane can be employed in comparison to prior work that used nitromethane as solvent (185 equiv). The present transformation provides high yields at relatively low temperatures and tolerates an array of functionality, including heterocycles and substantial steric encumbrance.
Palladium-catalyzed nitromethylation of aryl halides: An orthogonal formylation equivalent
Walvoord, Ryan R.,Berritt, Simon,Kozlowski, Marisa C.
supporting information; experimental part, p. 4086 - 4089 (2012/09/22)
An efficient cross-coupling reaction of aryl halides and nitromethane was developed with the use of parallel microscale experimentation. The arylnitromethane products are precursors for numerous useful synthetic products. An efficient method for their direct conversion to the corresponding oximes and aldehydes in a one-pot operation has been discovered. The process exploits inexpensive nitromethane as a carbonyl equivalent, providing a mild and convenient formylation method that is compatible with many functional groups.
