著者

Lu Lin Shunsuke Kataoka Kiichi Hirayama Ryozo Shibuya Kenji Watanabe Hiroyuki Morimoto Takashi Ohshima

出版者

The Pharmaceutical Society of Japan

雑誌

Chemical and Pharmaceutical Bulletin (ISSN:00092363)

巻号頁・発行日

vol.71, no.2, pp.101-106, 2023-02-01 (Released:2023-02-01)

参考文献数

53

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Catalytic control of chemoselectivity is crucial in the synthesis of highly functionalized compounds. Although there are reports of efficient chemoselective reactions of alcohols and amines as nucleophiles, there are no reports of the chemoselective activation of alcohols and amines as electrophiles. In this study, highly O- and N-selective electrophilic activation of allylic alcohols and amines was achieved in Pd-catalyzed direct allylic alkylation. Allylamines were inherently more reactive than allylic alcohols (N-selectivity). On the other hand, the addition of catalytic amounts of 9-phenanthreneboronic acid preferentially activated allylic alcohols over allylamines (O-selectivity). Density functional theory (DFT) calculations suggested that the N-selectivity is due to the selective activation of allylic amines with ammonium cations, and boronate formation accelerates the activation of allylic alcohols.

著者

Kazuhiro Morisaki Yuta Kondo Masanao Sawa Hiroyuki Morimoto Takashi Ohshima

出版者

公益社団法人日本薬学会

雑誌

Chemical and Pharmaceutical Bulletin (ISSN:00092363)

巻号頁・発行日

vol.65, no.11, pp.1089-1092, 2017-11-01 (Released:2017-11-01)

参考文献数

20

被引用文献数

1

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This note describes the construction of tetrasubstituted carbon stereocenters via palladium-catalyzed allylation of sp3 C–H bonds of 2,2,2-trifluoroethylamine derivatives. The presence of 2-pyridyl group of the imines derived from 1-substituted-2,2,2-trifluoroethylamine was key to promoting the reaction efficiently, allowing an access to a variety of 1-allylated 2,2,2-trifluoroethylamine derivatives with tetrasubstituted carbon stereocenters.

著者

吉田 美緒 本島 正人 大島 尚 ヨシダ ミオ モトジマ マサト オオシマ タカシ Mio YOSHIDA Masato MOTOJIMA Takashi OHSHIMA

出版者

東洋大学「エコ・フィロソフィ」学際研究イニシアティブ(TIEPh)事務局

雑誌

「エコ・フィロソフィ」研究 = Eco-philosophy (ISSN:18846904)

巻号頁・発行日

no.1, pp.129-149, 2007-03