Highly regio- and stereo-selective carbometallation reaction of fluorine-containing internal acetylenes with organocopper reagents |
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Authors: | Tsutomu Konno Takeshi Daitoh Atsushi Noiri Jungha Chae Takashi Ishihara Hiroki Yamanaka |
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Institution: | Department of Chemistry and Materials Technology, Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto 606-8585, Japan |
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Abstract: | The carbometallation reactions of fluoroalkylated internal alkynes with various organocopper reagents derived from organolithium, Grignard, and organozinc reagents were examined. All carbocupration reactions proceeded smoothly in a highly regio- and stereo-selective manner to give the corresponding vinylcopper intermediates. The intermediates reacted with H+ smoothly, leading to the trisubstituted alkenes in high to excellent yields, whereas they reacted only with strictly limited carbon electrophiles such as allyl-, crotyl-, methallyl bromide, etc, probably due to the low reactivity exerted by an electron-withdrawing fluoroalkyl group. Treatment of vinylcopper with iodine resulted in a high yield of the corresponding vinyl iodide, which was employed successfully for Suzuki-Miyaura and Sonogashira cross-coupling reactions. In addition, two key reactions, the carbocupration and the Suzuki-Miyaura cross-coupling reaction realized the first highly stereoselective total synthesis of anti-estrogen drug, panomifene. |
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Keywords: | Fluorinated materials Carbometallation Fluorinated alkynes |
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