Silicon Polonovski Reaction. Formation and Synthetic Application of α-Siloxy Amines

• Tokitoh Norihiro

  Department of Chemistry, Faculty of Science, The University of Tokyo

• Okazaki Renji

  Department of Chemistry, Faculty of Science, The University of Tokyo

書誌事項

タイトル別名

• Silicon Polonovski reaction. Formation and synthetic application of .ALPHA.-siloxy amines.

抄録

A new and versatile synthetic intermediate, α-siloxy amine was prepared in situ by the base-promoted rearrangement of a siloxyammonium salt obtained by treatment of a tertiary amine N-oxide with trialkylsilyl trifluoromethanesulfonate. The best combination of the base and silylating reagent was found to be methyllithium and t-butyldimethylsilyl trifluoromethanesulfonate. The reactions of α-siloxy amines with acyl halides and haloformates gave the corresponding amides and carbamates in moderate to good yields, respectively. Treatment of α-siloxy amines with acetic acid resulted in a direct dealkylation to free secondary amines. Fluoride induced alkylation of α-siloxy amines using alkyl halides as electrophiles leading to tertiary amines was also examined and demonstrated to be a new transalkylation method of amines.

収録刊行物

• Bulletin of the Chemical Society of Japan

  Bulletin of the Chemical Society of Japan 60 (9), 3291-3297, 1987

  公益社団法人 日本化学会

キーワード

• General Chemistry

詳細情報

• CRID: 1390001204127759744
• NII論文ID: 130001981742
• DOI: 10.1246/bcsj.60.3291
• ISSN: 13480634
• ISSN: 00092673
• Web Site: https://academic.oup.com/bcsj/article-pdf/60/9/3291/55724283/bcsj.60.3291.pdf
• 本文言語コード: en
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  • CiNii Articles
• 抄録ライセンスフラグ: 使用不可