Heteroatom-guided torquoselective olefination of alpha-oxy and alpha-amino ketones via ynolates |
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Authors: | Shindo Mitsuru Yoshikawa Takashi Itou Yasuaki Mori Seiji Nishii Takeshi Shishido Kozo |
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Institution: | Institute for Materials Chemistry and Engineering, Kyushu University, 6-1, Kasugakoen, Kasuga, Fukuoka 816-8580, Japan. shindo@cm.kyushu-u.ac.jp |
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Abstract: | Ynolates were found to react with alpha-alkoxy-, alpha-siloxy-, and alpha-aryloxyketones at room temperature to afford tetrasubstituted olefins with high Z selectivity. Since the geometrical selectivity was determined in the ring opening of the beta-lactone enolate intermediates, the torquoselectivity was controlled by the ethereal oxygen atoms. From experimental and theoretical studies, the high Z selectivity is induced by orbital and steric interactions rather than by chelation. In a similar manner, alpha-dialkylamino ketones provided olefins with excellent Z selectivity. These products can be easily converted into multisubstituted butenolides and gamma-butyrolactams in good yield. |
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