J . Org. Chem. 1999, 64, 1635-1639
1635
Dia ster eoselective Ep oxid a tion of Cycloh exen e Der iva tives by
Dioxir a n es Gen er a ted in Situ . Im p or ta n ce of Ster ic a n d F ield
Effects
Dan Yang,* Guan-Sheng J iao, Yiu-Chung Yip, and Man-Kin Wong
Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong
Received November 2, 1998
In this paper, diastereoselective epoxidation of substituted cyclohexenes (substrates 1-7) by
dioxiranes generated in situ from ketones and Oxone was systematically investigated. The results
revealed that the diastereoselectivity was determined by the steric and field effects of both dioxiranes
and substrates, and high diastereoselectivity can be achieved by tuning the ketone structure. Among
the ketones tested, 12 and 19 gave the best diastereoselectivities.
,10b-d,f,11b,12,15
9a,10c,e,14
In tr od u ction
bonding,9
dipole-dipole interactions,
torsional effects,1
3,16
and solvent effects.
9,10b-d,f,11b,12
For
1
Dioxiranes are synthetically useful oxidants for ep-
oxidation of olefins. While significant progress has been
epoxidation of a given olefin substrate, the convenient
2
method of generating dioxiranes in situ from ketones and
made in enantioselective epoxidation by chiral dioxi-
ranes,3 highly diastereoselective epoxidation remains
a challenge for organic synthesis. Several studies have
been carried out on diastereoselective epoxidation
with isolated dimethyldioxirane and methyl(trifluorom-
18-24
Oxone
makes it possible to screen as many dioxiranes
-8
as needed in order to achieve high diastereoselectivity.
Therefore, it becomes important to understand how the
9
-16
nature of dioxiranes controls the diastereoselectivity of
20,22
epoxidation.
We have systematically examined the
1
7
ethyl)dioxirane, and the diastereoselectivity was found
effect of ketone structures as well as the nature of
substrates on the diastereoselectivity of in situ dioxirane
epoxidation reactions. The detailed results are reported
herein.
to be determined by steric effects,9
a,10c,e,11a,12
hydrogen-
(
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1
0.1021/jo9821978 CCC: $18.00 © 1999 American Chemical Society
Published on Web 02/13/1999