Organic & Biomolecular Chemistry
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COMMUNICATION
Journal Name
DOI: 10.1039/D0OB01683G
OH
O
HO
OH
O
HO
OH
OH
O 1.87
HO
HO
O
O
HO
HO
HO
HO
ΔG (kcal/mol)
OMe
OH
1.89 Cu
1.91
O 1.93
2.10
O
HO
HO
O 1.92
O
2.12
OMe
1.86
OMe
OMe
2.23
1.93 Cu
2.19
2.12
O 1.93
1.94
2.05
1.95
OPh
Cu
Cu
2.61
30
25
OMe
2.52
1.89
2.95
1.92 Cu
2.11
I
TSRE4 (+28.2)
TSRE3 (+25.0)
OPh
2.52
I
I
TSRE3
TSRE4
TSOA
(+23.9)
20
TSRE2 (+21.6)
TSRE1 (+16.4)
OH
OH
INT2
(+22.1)
+KOPh
–KI
6
O
O
INT3OPh
(+20.0)
HO
HO
HO
OH
4
HO
O
HO
15
10
5
O 1.92
O
1.89
2.00
HO
1
OMe
OMe
2.28
2
+KOH
3
2.22
O
1.92
2.09
–KI
1.96
Cu
Cu
1.90
OMe
1.97
1.84
2.65
Cu
OH
TSRE1
HO
INT3OH
(+10.6)
2.64
2.14
I
TSRE2
OH
0
O
HO
INT1
(+0.0)
HO
OH
OH
OH
O 1.88
O
O
O
INT7 (–24.5)
INT6 (–35.3)
HO
HO
HO
HO
HO
HO
OMe
1.88 Cu
2.10
O
O
O
1.83
OMe
OMe
OMe
OH
Cu
HO
Cu
Cu
INT5 (–37.1)
INT4 (–42.8)
R
OPh
INT5 (R = OH)
INT6 (R = I)
Oxidative addition
Ligand exchange
Reductive elimination
INT4
INT7
Figure 1. DFT calculations on a model reaction between a simplified Cu(I)-methylglucoside complex and iodobenzene. Energy changes and bond lengths at the M06-
2X/SDD and 6-311+G*/SMD(water)//M06-2X/SDD and 6-31+G*/SMD(water) level of theory are shown in kcal/mol and Å, respectively.
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In summary, we have developed a robust process for the
hydroxylation of arenes in water, catalyzed by
a
copper(I)/sucrose system. The present reaction uses abundant
and inexpensive reagents (Cu2O, sucrose, K2CO3, and water) and
can be performed under atmospheric conditions without
undesired side reactions. We have identified the dual role of
sucrose, which consists of a) enhancing the reactivity of the
catalyst, and b) increasing the solubility of the substrates in
water. Furthermore, a selective reaction pathway was proposed
based on a combination of experimental results and DFT
calculations. Further investigations in order to apply similar
strategies to other carbon–heteroatom and carbon–carbon
bond-forming reactions are currently in progress.
This work was supported by JSPS KAKENHI grants JP19K06992
and JP20K15273, the Uehara Memorial Foundation, the Takeda
Science Foundation, the FUGAKU Trust for Medicinal Research,
and the Naito Foundation. Computational calculations were
performed using the resources of the Research Center for
Computational Science at Okazaki, Japan.
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Conflicts of interest
There are no conflicts to declare.
Notes and references
1
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For details, see the ESI.
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4 | J. Name., 2012, 00, 1-3
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