A series of C
2 symmetric chiral ketones
were designed and synthesized for catalytic asymmetric
epoxidation of unfunctionalized olefins. Among those ketones
screened, (R)-7, (R)-9, and
(R)-10 were found
to be highly efficient catalysts for epoxidation of
trans-stilbenes with enantioselectivities in the range of
84−95%. Convincing evidence was provided for a spiro transition state
of dioxirane epoxidation. Through the
18O-labeling experiment, chiral dioxiranes were found to be
the intermediates in chiral ketone catalyzed
epoxidation reactions.
Kinetic resolution of acyclic secondary allylic silyl ethers by chiral dioxiranes generated in situ from chiral ketones (R)-1 and (R)-2 and Oxone was investigated. An efficient and catalytic method has been developed for kinetic resolution of those substrates with a CCl(3), tert-butyl, or CF(3) group at the alpha-position. In particular, high selectivities (S up to 100) were observed for kinetic resolutions of racemic alpha-trichloromethyl allylic silyl ethers 7 and 9-15 catalyzed by ketones (R)-2. Both the recovered substrates and the resulting epoxides were obtained in high enantiomeric excess. On the basis of steric and electrostatic interactions between the chiral dioxiranes and the racemic substrates, a model was proposed to rationalize the enantioselectivities and diastereoselectivities in the chiral ketone-catalyzed kinetic resolution process.
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