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Palladium-Catalyzed Diarylation of Isocyanides with Tetraarylleads for the Selective Synthesis of Imines and α-Diimines

発表形態:
原著論文
主要業績:
主要業績
単著・共著:
共著
発表年月:
2019年09月
DOI:
10.1021/acs.joc.9b01639
会議属性:
指定なし
査読:
有り
リンク情報:

日本語フィールド

著者:
Tran, Cong Chi; Kawaguchi, Shin Ichi; Kobiki, Yohsuke; Matsubara, Hitomi; Tran, Dat Phuc; Kodama, Shintaro; Nomoto, Akihiro; Ogawa, Akiya
題名:
Palladium-Catalyzed Diarylation of Isocyanides with Tetraarylleads for the Selective Synthesis of Imines and α-Diimines
発表情報:
Journal of Organic Chemistry 巻: 84 号: 18 ページ: 11741 - 11751
キーワード:
概要:
© 2019 American Chemical Society. Using tetraaryllead compounds (PbAr4) as arylating reagents, isocyanides undergo selective diarylation in the presence of palladium catalysts such as Pd(OAc)2 or Pd(PPh3)4 to afford imines and/or α-diimines based on the isocyanide employed. With aliphatic isocyanides, imines are obtained preferentially, whereas α-diimines are formed in the case of electron-rich aromatic isocyanides. The differences in imine/α-diimine selectivity can be attributed to the stability of imidoylpalladium intermediates formed in this catalytic reaction. Compared with other arylating reagents, tetraaryllead compounds are excellent candidates for use in the selective transformations to imines and/or α-diimines, especially in terms of inhibiting the oligomerization of isocyanides, which results in a lower product selectivity in many transition-metal-catalyzed reactions of isocyanides.
抄録:

英語フィールド

Author:
Tran, Cong Chi; Kawaguchi, Shin Ichi; Kobiki, Yohsuke; Matsubara, Hitomi; Tran, Dat Phuc; Kodama, Shintaro; Nomoto, Akihiro; Ogawa, Akiya
Title:
Palladium-Catalyzed Diarylation of Isocyanides with Tetraarylleads for the Selective Synthesis of Imines and α-Diimines
Announcement information:
Journal of Organic Chemistry Vol: 84 Issue: 18 Page: 11741 - 11751
An abstract:
© 2019 American Chemical Society. Using tetraaryllead compounds (PbAr4) as arylating reagents, isocyanides undergo selective diarylation in the presence of palladium catalysts such as Pd(OAc)2 or Pd(PPh3)4 to afford imines and/or α-diimines based on the isocyanide employed. With aliphatic isocyanides, imines are obtained preferentially, whereas α-diimines are formed in the case of electron-rich aromatic isocyanides. The differences in imine/α-diimine selectivity can be attributed to the stability of imidoylpalladium intermediates formed in this catalytic reaction. Compared with other arylating reagents, tetraaryllead compounds are excellent candidates for use in the selective transformations to imines and/or α-diimines, especially in terms of inhibiting the oligomerization of isocyanides, which results in a lower product selectivity in many transition-metal-catalyzed reactions of isocyanides.


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