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Dimethyldioxirane Oxidation of Enamines: First Spectral Evidence for Enamine Oxides by Stabilization through N ‐Silylation
Author(s) -
Adam Waldemar,
Ahrweiler Michael,
Paulini Klaus,
Reißig Hans–Ulrich,
Voerckel Volkmar
Publication year - 1992
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19921251217
Subject(s) - chemistry , dimethyldioxirane , enamine , ketone , acetone , medicinal chemistry , trimethylsilyl , silylation , nitrogen atom , alkyl , organic chemistry , aldol reaction , catalysis
The oxygen transfer to the enamines 1a–f by dimethyldioxirane (DMD) in acetone solution leads to the α–amino epoxides 2a–f . The stability of the α–amino epoxides 2a–f depends only on the type of substitution at the nitrogen atom. Thus, while the epoxides 2a, b could be characterized spetroscopically, the epoxidation of the enamines 1c–f resulted in the corresponding α–amino ketone 3c (hydride shift) and the amides 4d–f (alkyl shift). The α‐[bis(trimethylsilyl)]amino epoxides 2a, b represent the first observable enamine oxides and emphasize the value of stabilizing such labile epoxides through disilylation of the enamine nitrogen atom.