Stereoselective Amine Addition to Six-Membered Cyclic Nitronates Promoted by Silyl Triflate

Six‐membered cyclic nitronates couple with amines or their N‐silyl derivatives in a diastereoselective fashion to give 3‐amino‐substituted nitroso acetals in 53–89 % yield through silyl triflate electrophilic catalysis. Stereodifferentiation of this process is determined by thermodynamic control, wh...

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Bibliographic Details
Published in:European journal of organic chemistry 2013-09, Vol.2013 (25), p.5670-5677
Main Authors: Mikhaylov, Andrey A., Dilman, Alexander D., Khomutova, Yulia A., Arkhipov, Dmitry E., Korlyukov, Alexander A., Ioffe, Sema L.
Format: Article
Language:English
Subjects:
Amines
C-C coupling
Diastereoselectivity
Nucleophilic addition
Reaction mechanisms
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Summary:Six‐membered cyclic nitronates couple with amines or their N‐silyl derivatives in a diastereoselective fashion to give 3‐amino‐substituted nitroso acetals in 53–89 % yield through silyl triflate electrophilic catalysis. Stereodifferentiation of this process is determined by thermodynamic control, which is realized due to reversibility of amine addition and a decreased nitrogen inversion barrier in the resulting nitroso acetals. Selected chemical transformations of nitroso acetals were examined. N‐Silylamines add to six‐membered nitronates with high diastereoselectivity. The reaction follows an original mechanism in which thermodynamic control plays the key role.
ISSN:1434-193X
1099-0690
DOI:10.1002/ejoc.201300511