Ru3(CO)12- and Rh4(CO)12-Catalyzed Reactions of Pyridylolefins or N-(2-Pyridyl)enamines with CO and Olefins. Carbonylation at Olefinic C-H Bonds

Naoto Chatani, Yutaka Ishii, Yutaka Ie, Fumitoshi Kakiuchi, Shinji Murai

研究成果: Article査読

62 被引用数 (Scopus)

抄録

This paper describes a study of the Ru3(CO)12-catalyzed carbonylation at an olefinic C-H bond. The reaction of pyridylolefins with CO and ethylene in the presence of a catalytic amount of Ru3-(CO)12 in toluene results in propionylation at an olefinic C-H bond in pyridylolefins. The carbonylation occurs regioselectively at a position γ to the pyridine nitrogen. Transition-metal complexes other than Ru3(CO)12, that have thus far been examined exhibit no catalytic activity, and ethylene serves as the only olefin. A similar tendency has been noted in the previously reported carbonylation at a C-H bond in the benzene ring of pyridylbenzenes. This reaction can be also applied to N-(2-pyridyl)enamines, in which an olefin unit is separated from the pyridine ring by an sp3-nitrogen atom. The reaction of N-(2-pyridyl)enamines with CO and ethylene gives the corresponding ethyl ketones as the coupling products. Interestingly, Rh4(CO)12 also shows high catalytic activity in the case of N-(2-pyridyl)enamines. In addition, olefins such as propene, 1-hexene, 3,3-dimethyl-1-butene, styrene, cyclopentene, acryl acid methyl ester, ethyl vinyl ether, and trimethylvinylsilane can also be used. This is in sharp contrast to the case of the carbonylation at a C-H bond in pyridylbenzenes reported previously and to the results of pyridylolefins as mentioned above, where Ru3(CO)12 is the only active catalyst and hexene cannot substitute for ethylene.

本文言語English
ページ(範囲)5129-5136
ページ数8
ジャーナルJournal of Organic Chemistry
63
15
DOI
出版ステータスPublished - 1998 7 24
外部発表はい

ASJC Scopus subject areas

  • 有機化学

フィンガープリント

「Ru<sub>3</sub>(CO)<sub>12</sub>- and Rh<sub>4</sub>(CO)<sub>12</sub>-Catalyzed Reactions of Pyridylolefins or N-(2-Pyridyl)enamines with CO and Olefins. Carbonylation at Olefinic C-H Bonds」の研究トピックを掘り下げます。これらがまとまってユニークなフィンガープリントを構成します。

引用スタイル