Synthesis 2020; 52(22): 3461-3465
DOI: 10.1055/s-0040-1707191
paper
© Georg Thieme Verlag Stuttgart · New York

Efficient Synthesis of O-tert-Propargylic Oximes via Nicholas Reaction

a  Research and Analytical Center for Giant Molecules, Graduate School of Science, Tohoku University, 6-3 Aramaki Aza Aoba, Aoba-ku, Sendai 980-8578, Japan   Email: itaru-n@tohoku.ac.jp
,
Keigo Shiga
b  Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki Aza Aoba, Aoba-ku, Sendai 980-8578, Japan
,
Mao Suzuki
b  Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki Aza Aoba, Aoba-ku, Sendai 980-8578, Japan
,
Masahiro Terada
b  Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki Aza Aoba, Aoba-ku, Sendai 980-8578, Japan
› Author Affiliations
This work was supported by JSPS KAKENHI Grant Number JP16H00996 in Precisely Designed Catalysts with Customized Scaffolding and JP20H02731 (Grant-in-Aid for Scientific Research (B)) from MEXT Japan.
Further Information

Publication History

Received: 26 May 2020

Accepted after revision: 09 June 2020

Publication Date:
21 July 2020 (online)


Abstract

A synthetic protocol to access O-tert-propargylic oximes derived from tertiary propargylic alcohols was established via Nicholas reaction. Thus, BF3·OEt2-mediated reaction between the dicobalt hexacarbonyl complex of tert-propargylic alcohols and p-nitrobenzaldoxime followed by decomplexation with cerium(IV) ammonium nitrate afforded the corresponding O-tert-propargylic oximes in good to high yields. The obtained O-tert-propargylic oximes were effectively converted into heterocycles, such as four-membered cyclic nitrones, oxazepines, and isoxazolines, by using π-Lewis acidic catalysts.

Supporting Information

 
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