"Syn effect" in nucleophilic addition of amines to 1,3-dienyl sulfone and ethyl (E)-2,4-pentadienoate

フォーマット:

論文

責任表示:

Yamazaki, Masao ; Guha, Samar Kumar ; Ukaji, Yutaka ; Inomata, Katsuhiako

言語:

英語

出版情報:

The Chemical Society of Japan = 日本化学会, 2008-01-01

著者名:

• Yamazaki, Masao
• Guha, Samar Kumar
• Ukaji, Yutaka
• Inomata, Katsuhiako

掲載情報:

Bulletin of the Chemical Society of Japan

ISSN:

0009-2673      

巻:

81

通号:

6

開始ページ:

740

終了ページ:

753

バージョン:

publisher

概要:

The stereochemistry of nucleophilic addition of amines to (E)-1-tosyl-1,3-butadiene was investigated. The Z/E ratios of the resulting allylic sulfones varied with amines, solvents, temperature, and concentration. When diethylamine was reacted in low concentration at high temperature, the corresponding sterically unfavorable (Z)-4-amino-2-butenyl sulfone was preferentially obtained. The stereochemistry of nucleophilic addition of amines … to ethyl (E)-2,4-pentadienoate, which possesses an ester group as a conjugated electron-withdrawing group instead of a p-toluenesulfonyl (Ts) group, was also found to realize similar high Z selectivity. The predominant formation of Z isomers in both cases was rationalized by a “syn effect,” which might be mainly due to n⁄σ→π* interaction and/or 6π-electron homoaromaticity. 続きを見る

URL:

http://hdl.handle.net/2297/38203