Alkenylation of 1- and 2-Naphthols by Using Magnesium Alkylidene Carbenoids as Electrophilic Alkenylating Agents

Tsutomu Kimura; Masaya Watanabe; Gaku Kashiwamura; Jo Sakurada; Tsuyoshi Satoh

doi:10.1055/s-0032-1318132

Synthesis, Table of Contents

Synthesis 2013; 45(5): 659-667
DOI: 10.1055/s-0032-1318132

paper

Alkenylation of 1- and 2-Naphthols by Using Magnesium Alkylidene Carbenoids as Electrophilic Alkenylating Agents

Authors

Tsutomu Kimura

^aDepartment of Chemistry, Faculty of Science, Tokyo University of Science, 12 Ichigaya-funagawara-machi, Shinjuku-ku, Tokyo 162-0826, Japan
Masaya Watanabe

^bGraduate School of Chemical Sciences and Technology, Tokyo University of Science, 12 Ichigaya-funagawara-machi, Shinjuku-ku, Tokyo 162-0826, Japan Fax: +81(3)52614631 Email: tsatoh@rs.kagu.tus.ac.jp
Gaku Kashiwamura

^bGraduate School of Chemical Sciences and Technology, Tokyo University of Science, 12 Ichigaya-funagawara-machi, Shinjuku-ku, Tokyo 162-0826, Japan Fax: +81(3)52614631 Email: tsatoh@rs.kagu.tus.ac.jp
Jo Sakurada

^bGraduate School of Chemical Sciences and Technology, Tokyo University of Science, 12 Ichigaya-funagawara-machi, Shinjuku-ku, Tokyo 162-0826, Japan Fax: +81(3)52614631 Email: tsatoh@rs.kagu.tus.ac.jp
Tsuyoshi Satoh*

^aDepartment of Chemistry, Faculty of Science, Tokyo University of Science, 12 Ichigaya-funagawara-machi, Shinjuku-ku, Tokyo 162-0826, Japan

^bGraduate School of Chemical Sciences and Technology, Tokyo University of Science, 12 Ichigaya-funagawara-machi, Shinjuku-ku, Tokyo 162-0826, Japan Fax: +81(3)52614631 Email: tsatoh@rs.kagu.tus.ac.jp

Abstract

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Abstract

1- and 2-Naphthols were successfully alkenylated in a regioselective manner by treating the corresponding lithium 1- and 2-naphtholates with magnesium alkylidene carbenoids. The magnesium alkylidene carbenoids were generated in situ by a sulfoxide–magnesium exchange reaction of 1-chlorovinyl 4-tolyl sulfoxides with isopropylmagnesium chloride. The reaction of magnesium alkylidene carbenoids with lithium 2-naphtholates took place at the 1-position of the naphthyl ring to give 1-(alk-1-enyl)-2-naphthols in respectable yields. The alkenylation of 1-naphthols proceeded at the 2-position of the naphthol ring to give 2-(alk-1-enyl)-1-naphthols in yields of 56–67%. In contrast to the reaction of lithium naphtholates with magnesium alkylidene carbenoids, the reaction of lithium phenolates gave low yields of the corresponding alk-1-enyl aryl ethers.

Key words

alkenation - phenols - carbenoids - sulfoxides - alkenes - arenes - organometallic reagents

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References

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