Sequential Acylation/Silylation/Hetero‐Claisen Rearrangement of Nitroalkanes for the Synthesis of Protected Hydroxyoxime Derivatives

Sequential Acylation/Silylation/Hetero‐Claisen Rearrangement of Nitroalkanes for the Synthesis of Protected Hydroxyoxime Derivatives Full article

Journal

European Journal of Organic Chemistry
ISSN: 1434-193X , E-ISSN: 1099-0690

Output data

Year: 2021, Volume: 2021, Number: 22, Pages: 3197-3213 Pages count : 17 DOI: 10.1002/ejoc.202100469

Authors

Antonova Yulia A. ^1,2 , Ioffe Sema L. ¹ , Sukhorukov Alexey Yu. ¹ , Tabolin Andrey A. ¹

Affiliations

1	N. D. Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Leninsky prosp. 47 Moscow 119991 Russia
2	Department of Chemistry M. V. Lomonosov Moscow State University Leninskie gory 1 Moscow 119991 Russia

Sequential acylation-silylation of nitroalkanes leads to O-silylated α-acyloxyoximes in high yields. The first step of the reaction involves deprotonation of nitro compound with sodium hydride promoted by DBU or alcohol/15-crown-5 system followed by treatment with acyl chloride. In situ generated acyl nitronate is further silylated by silyl triflate that triggers hetero-Claisen [3,3]-rearrangement within N-acyloxyenamine moiety furnishing orthogonally protected oxime derivatives. The procedure has large substrate scope for both nitroalkanes and acylating agents (acyl chlorides, chloroformates) and allows tuning of reaction conditions depending on the particular type of substrate. Application of obtained oxime derivatives in organic synthesis is demonstrated.

Antonova Y.A. , Ioffe S.L. , Sukhorukov A.Y. , Tabolin A.A.
Sequential Acylation/Silylation/Hetero‐Claisen Rearrangement of Nitroalkanes for the Synthesis of Protected Hydroxyoxime Derivatives
European Journal of Organic Chemistry. 2021. V.2021. N22. P.3197-3213. DOI: 10.1002/ejoc.202100469 WOS Scopus OpenAlex

Web of science:	WOS:000664610800008
Scopus:	2-s2.0-85108286041
OpenAlex:	W3161553635

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OpenAlex	2
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Web of science	2