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

Itaru Nakamura; Keigo Shiga; Mao Suzuki; Masahiro Terada

doi:10.1055/s-0040-1707191

Synthesis, Table of Contents

Synthesis 2020; 52(22): 3461-3465
DOI: 10.1055/s-0040-1707191

paper

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

Itaru Nakamura ∗

^aResearch 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

^bDepartment of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki Aza Aoba, Aoba-ku, Sendai 980-8578, Japan

,

Mao Suzuki

^bDepartment of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki Aza Aoba, Aoba-ku, Sendai 980-8578, Japan

,

Masahiro Terada

^bDepartment of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki Aza Aoba, Aoba-ku, Sendai 980-8578, Japan

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Abstract

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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.

Key words

Nicholas reaction - alkynes - tertiary alcohols - heterocycles - gold catalysts - spirocycles

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