877869-53-9Relevant academic research and scientific papers
Heteroatom-guided torquoselective olefination of α-oxy and α-amino ketones via ynolates
Shindo, Mitsuru,Yoshikawa, Takashi,Itou, Yasuaki,Mori, Seiji,Nishii, Takeshi,Shishido, Kozo
, p. 524 - 536 (2008/09/20)
Ynolates were found to react with α-alkoxy-, α-siloxy-, and α -aryloxyketones at room temperature to afford tetrasubstituted olefins with high Z selectivity. Since the geometrical selectivity was determined in the ring opening of the β-lactone enolate intermediates, the torquoselectivity was controlled by the ethereal oxygen atoms. From experimental and theoretical studies, the high Z selectivity is in duced by orbital and steric interactions rather than by chelation. In a similar manner, α-dialkylamino ketones provided olefins with excellent Z selectivity. These products can be easily converted into multisubstituted butenolides and γ-butyrolactams in good yield.
