Chemistry of N,N-Bis(silyloxy)enamines. 3. N,N-Bis(silyloxy)enamines as β-C-Nucleophiles in Reaction with Acetals Mediated by Trimethylsilyl Trifluoromethanesulfonate1

Chemistry of N,N-Bis(silyloxy)enamines. 3. N,N-Bis(silyloxy)enamines as β-C-Nucleophiles in Reaction with Acetals Mediated by Trimethylsilyl Trifluoromethanesulfonate1 Full article

Journal

Journal of Organic Chemistry
ISSN: 1520-6904 , E-ISSN: 0022-3263

Output data

Year: 2000, Volume: 65, Number: 25, Pages: 8826-8829 Pages count : 4 DOI: 10.1021/jo0009402

Authors

Dilman Alexander D. ¹ , Lyapkalo Il'ya M. ¹ , Ioffe Sema L. ¹ , Strelenko Yury A. ¹ , Tartakovsky Vladimir A. ¹

Affiliations

1	N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 117913 Moscow, Russian Federation iof@cacr.ioc.ac.ru

Silylation of nitro compounds may afford silyl derivatives of two different types, namely, silyl nitronates and N,N-bis(silyloxy)enamines (BENA). Whereas thoroughly studied transformations of silyl nitronates constitute a substantial part of the chemistry of aliphatic nitro compounds, 2 the reactivity of BENA remains scarcely investigated. 3 At the same time, these derivatives may become attractive intermediates in organic synthesis, especially in light of the convenience of their preparation and handling. 4 Recently, we demonstrated that terminal BENA 1 behave as formal β-C-electrophiles in C,C-cross-coupling reactions with stabilized carbanions leading to corresponding oximes 3 through the intermediacy of conjugated nitroso alkenes 2 (Scheme 1). 5 Since the convenient conversion of oximes 3 into nitro compounds 4 has been reported, 6 the reaction sequence depicted in eq 1 could be considered as a simple way to introduce the nucleophile into the α-methyl group of starting nitro alkanes via their double silylation. However, BENA 1 turned out to be “chemical chameleons”. Under certain conditions, they could react at the β-carbon atom not only with nucleophiles, but also with electrophiles, furnishing corresponding nitro compounds 6 after protolysis of initially formed silyl nitronates 5 (Scheme 1, eq 2). Thus, it becomes feasible to incorporate the electrophile into α-methyl substituent of starting nitro compounds through their double silylation. Herein we disclose the first C,C-cross-coupling reaction of BENA 1 with electrophiles generated from acetals giving rise to nitro compounds 6.

Dilman A.D. , Lyapkalo I.M. , Ioffe S.L. , Strelenko Y.A. , Tartakovsky V.A.
Chemistry of N,N-Bis(silyloxy)enamines. 3. N,N-Bis(silyloxy)enamines as β-C-Nucleophiles in Reaction with Acetals Mediated by Trimethylsilyl Trifluoromethanesulfonate1
Journal of Organic Chemistry. 2000. V.65. N25. P.8826-8829. DOI: 10.1021/jo0009402 Scopus OpenAlex

Scopus:	2-s2.0-0034670629
OpenAlex:	W2950893526

DB	Citing
OpenAlex	20
Scopus	23