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Solid-phase Synthesis of [4.4] Spirocyclic Oximes
Published on: February 6, 2019
Thiyl radical-mediated cyclization of ω-alkynyl O-tert-butyldiphenylsilyloximes
Nina Shibata1, Takahisa Tsuchiya1, Yoshimitsu Hashimoto1
1Showa Pharmaceutical University, 3-3165, Higashi-Tamagawagakuen, Machida, Tokyo, Japan. tamura@ac.shoyaku.ac.jp.
Abstract:
ω-Alkynyl O-tert-butyldiphenylsilyloximes, upon treatment with odorless 4-tert-butylbenzenethiol in the presence of azobisisobutyronitrile (AIBN) in refluxing benzene, underwent addition of a thiyl radical to the alkynyl group followed by radical cyclization of the corresponding vinyl radical onto the O-silyloxime moiety to give cyclic O-silylhydroxylamines in good yields. The reactivity of O-silyloximes in radical cyclization was similar to or even higher than that of O-benzyloximes. Facile removal of the silyl group of the cyclization products leading to hydroxylamines and nitrone formation of the hydroxylamines were also demonstrated.
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