C-C Coupling of Acyclic Nitronates with Silyl Ketene Acetals under Silyl Triflate Catalysis: Reactivity Umpolung of Aliphatic Nitro Compounds

TBSOTf‐promoted C–C coupling of alkyl and trialkylsilyl nitronates with silyl ketene acetals yields functionalized nitroso acetals. This conversion may serve as a new simple procedure to reverse the conventional reactivity of aliphatic nitro compounds. Preliminary results on the hydrogenation of nit...

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Bibliographic Details
Published in:European journal of organic chemistry 2012-06, Vol.2012 (18), p.3377-3384
Main Authors: Smirnov, Vladimir O., Khomutova, Yulia A., Tartakovsky, Vladimir A., Ioffe, Sema L.
Format: Article
Language:English
Subjects:
Amino­ acids
C-C coupling
Hydrogenation
Nitro compounds
Umpolung
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Summary:TBSOTf‐promoted C–C coupling of alkyl and trialkylsilyl nitronates with silyl ketene acetals yields functionalized nitroso acetals. This conversion may serve as a new simple procedure to reverse the conventional reactivity of aliphatic nitro compounds. Preliminary results on the hydrogenation of nitroso acetals into amino acids derivatives, as well as TFA‐catalyzed transformations of nitroso acetals, are examined to prove the possible utility of this umpolung procedure. A very simple approach for umpolung of the conventional reactivity of nitroalkanes through their activation by silylation offers a convenient and efficient strategy for their C–C coupling with π‐nucleophiles. Both primary (8 examples) and secondary (4 examples) nitroalkanes may be involved in coupling with silyl ketene acetals (4 examples) to provide a concise route to substituted β‐amino acids.
ISSN:1434-193X
1099-0690
DOI:10.1002/ejoc.201200239