- Microwave-assisted rapid dehydration of aldoximes to nitriles on a solid support
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p-toluenesulfonyl chloride has been proved out to be an efficient reagent for conversion of aldoximes to the corresponding nitriles under microwave irradiation. Extending the procedure to ketoximes, a 20-40% yield of Beckmann rearranged product was obtained.
- Ghiaci,Bakhtiari
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p. 1803 - 1807
(2007/10/03)
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- Organoaluminum-Promoted Beckmann Rearrangement of Oxime Sulfonates
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The Beckmann rearrangement of oxime sulfonates with simultaneous nucleophilic trapping of the intermediary iminocarbocation by organoaluminum reagents is described.This process provides a new and highly efficient route to imino thioethers, imino selenoethers, imino nitriles, and α-alkylated amines starting from oxime sulfonates by the use of dialkylaluminum thiolates, selenolates, diethylaluminum chloride-trimethylsilyl cyanide, and trialkylaluminum-diisobutylaluminum hydride systems, respectively.The present organoaluminum-promoted Beckmann rearrangement of oxime sulfonates has been successfully applied to the synthesis of naturally occuring alkaloids, pumiliotoxin C and solenopsin A and B, in stereoselective fashion.Moreover, α,α-dialkylation of amines can be realized by the successive treatment of oxime sulfonates with trialkylaluminum followed by allylic or propargylic Grignard reagents in synthetically useful yields.
- Maruoka, Keiji,Miyazaki, Tohru,Ando, Mamoru,Matsumura, Yasushi,Sakane, Soichi,et al.
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p. 2831 - 2843
(2007/10/02)
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