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References and notes
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N
4 (30 mol%)
(R,R)-3d
8%, 34% ee
+
(S,S)-2a
91%, 3% ee
p-CF3C6H4COCl (0.65 equiv.)
iPr2NEt (0.5 equiv.)
d,l-2a
EtCN, -78 oC, 1 h
Scheme 1.
uct 3e and unreacted alcohol 2b with high enantioselec-
tivities (Table 2, entry 2). In the case of the reactions of
trans-cyclohexanediol and trans-cyclopentanediol, the
use of p-chlorobenzoyl chloride as an acylation reagent
resulted in slightly higher selectivity factors (Table 2,
entries 4 and 6). The other diols containing heteroatoms
were also kinetically resolved in moderate selectivities
(Table 2, entries 7 and 8).
The kinetic resolution of d,l-hydrobenzoin using the
benzylether derivative of quinidine8 4 in place of 1b
was attempted. The reaction under optimized reaction
conditions in the presence of 30 mol % of 4 was sluggish
relative to the reaction using 1b and gave the monoacyl-
ated product with 34% ee (s = 2). These results indicate
that the phosphinite moiety is essential for attaining a
highly enantioselective monoacylation (Scheme 1).
2288; Kano, T.; Sasaki, K.; Maruoka, K. Org. Lett. 2005, 7,
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´
1347–1349; Dalaigh, C. O.; Hynes, S. J.; Maher, D. J.;
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In summary, we have demonstrated that the phosphinite
derivative of quinidine catalyzed the kinetic resolution
of C2-symmetric d,l-1,2-diols to produce the monoacyl-
ated product and unreacted diol with good to excellent
selectivities. Further applications of the amine-phosphi-
nite catalyst for the kinetic resolution of other racemic
compounds are under way in our laboratory.
Acknowledgement
6. Kagan, H. B.; Fiaud, J. C. Top. Stereochem. 1988, 18, 249–
330.
This work was supported by a Grant-in-Aid for the 21st
Century COE Program by the Ministry of Education,
Culture, Sports, Science, and Technology, Japan.
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