- One-step conversion to tertiary amines: InBr3/Et3SiH-mediated reductive deoxygenation of tertiary amides
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We have developed a simple and practical procedure for a direct reductive conversion from a variety of tertiary amides to the corresponding tertiary amines using an InBr3/Et3SiH reducing system. This reducing system can be applied to the reduction of a secondary amide and provides a more efficient alternative to conventional methods that use aluminum and boron hydrides.
- Sakai, Norio,Fujii, Kohji,Konakahara, Takeo
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scheme or table
p. 6873 - 6875
(2009/04/07)
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- Deprotonation de N-oxydes d'amines aliphatiques: schema reactionnel general et nouvelle synthese de pyrrolidines
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Amine oxides, 1, 5, 10, 15, 21, 23, when treated by lithium diisopropylamide undergo deprotonation.Monodeprotonation gives rise either to secondary amines and benzaldehyde resulting from the hydrolysis of an intermediate immonium (I) or to hydroxylamines via a Stevens-like rearrangement observed for the first time on an amine oxide.Double deprotonation gives an immonium ylid (Y) which, depending upon the structure of the initial tertiary amine yields either "head to head" piperazines (biradical-like behavior of (DD)) or aziridines.The immonium ylid (Y5) derived from trimethylamine oxide, whose formation and reactivity are reported for the first time, has remarkable property of undergoing cycloaddition reactions with unactivated olefins, leading to a new and efficient synthesis of various pyrrolidines.
- Beugelmans, Rene,Benadjila-Iguertsira, Leila,Chastanet, Jacqueline,Negron, Guillermo,Roussi, Georges
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p. 725 - 734
(2007/10/02)
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- 10. Nucleophile Aminoalkylierung mit Thiopivalamiden
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Of the twelwe thioamides 7a-e and 8a-g, only N,N-dimethylthiopivalamide (7a) could be metallated at the CH-group in α-position to the N-atom.The reagent 9 thus obtained (Table 1) reacts in high yields with primary haloalkanes, with aldehydes, and with non-enolizable ketones (Table 2).As shown in Scheme 1, the products can be hydrolyzed to pivalamides, cleaved to secondary amines, or reduced to neopentylamines (see 18/19, 15/equation (4) and (5), and 16/20, respectively).
- Lubosch, Winfried,Seebach, Dieter
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p. 102 - 116
(2007/10/02)
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