Journal of the American Chemical Society
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were prepared by direct oxidative coupling methods. On the basis
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of kinetic studies an oxidative radicalꢀanion coupling mechanism
was proposed. The optically instability of substituted BINOLs in
the presence of metals was studied, offering new insights into the
chemistry of BINOLs. Overall, the work suggests that the use of
chiral phosphate anions as ligands may provide a general platform
for the application of chiral iron catalysts in asymmetric syntheꢀ
sis.
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9
Figure 7. Enantioselective oxidative crossꢀcoupling of 2ꢀ
naphtols.a
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
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60
Fe[(R)ꢀL9]3
(3c, 2.5 mol %)
OH
R2
2a
+
4
+
+
conditions
OH
OH
OH
1b 1j
ꢀ (1 equiv)
R2
5
1
(1 equiv)
2a 4 5
coupling ratios [
:
:
]
OH
OH
OH
OH
OH
OH
OH
OH
iPr
Br
C4H9
C8H17
[3:1:2]
[1:6:5]
, 41%, 92:8 er
[1:2:4]
5c
, 46%, 96:4 er
[1:5:7]
5d, 43%, 89:11 er
5a
5b
(R)ꢀ , 34%, 87:13 er
(32%, 85:15 er)b
OH
OH
OH
OH
OH
iPr
OH
C4H9O
O
[1:8:8]
, 33%, 89:11 er
[1:1:3]
, 43%, 90:10 er
[1:4:5]
, 38%, 88:12 er
5g
5f
5e
OH
OH
OH
OH
OH
OH
HO
CF3
MeO
[3:1:2]
[1:1:3]
[2:1:4]
5j
(R)ꢀ , 53%, 81:19 er
CF3
5h
5i
(R)ꢀ , 33%, 86:14 er
, 48%, 86:14 er
(36%, 84:16 er)c
(54%, 83:17 er)c
aUnless otherwise noted, reactions were performed on a 0.05ꢀ
b
c
mmol scale; the reaction was performed on a gram scale; the
reaction was performed on a 0.5 mmol scale.
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ASSOCIATED CONTENT
Supporting Information
(9) (a) Zbieg, J. R.; Yamaguchi, E.; McInturff, E. L.; Krische, M. J.
Science 2012, 336, 324ꢀ327. (b) Rauniyar, V.; Wang, Z. J.; Burks, H. E.;
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Full experimental procedures, characterization data, and NMR
spectra is available free of charge via the Internet at
AUTHOR INFORMATION
Corresponding Author
Notes
The authors declare no competing financial interests.
ACKNOWLEDGMENT
This research was supported by the United States – Israel Biꢀ
national Science Foundation (BSF, grant No. 2012068). We thank
Mr. Mark Levin (UC Berkeley) for helpful comments during the
preparation of this manuscript.
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