Electronic Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2013
Heterogeneous and Homogeneous Chiral Cu(II) Catalysis in
Water: Enantioselective Boron Conjugate Additions to
Dienones and Dienoesters
_
Taku Kitanosono, Pengyu Xu and Shu Kobayashi*
Department of Chemistry, School of Sciences, The University of Tokyo,
Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
Electronic Supplementary Information
For Additional Table, Schemes, and Figures
Table S-1 Additions to Trienone
O
+
Ph
6
O
Cu Salt (5 mol%)
L1 (6 mol%)
2
(1.6 equiv)
O
+
O
OH
Ph
OH
7a
NaBO 3
H 2O, 5 oC, 12 h
OH
+
Ph
Ph
7b
7c
Entr Cu salt
y
Yield (%)
7a/7b/7c
E.r.
1
Cu(OH)2
71
< 1/74/26
86:14 (7b)
2a
Cu(OH)2
86
> 99/< 1/< 1
96:4 (7a)
3
Cu(OAc)2
87
> 99/< 1/< 1
95.5:4.5 (7a)
73:27 (7c)
a
6 mol% AcOH was added.
S-1
Electronic Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2013
O
O
R1
B 2(pin) 2
R2
B(pin)
R1
O
R2
*
R'
R1
R2
*
or
O
B(pin)
R1
O
* R2
R'
R1
* R2
Scheme S-1 Boron Conjugate Addition to α,β,γ,δ-Unsaturated Dienones and Dienoesters
4a
O
Cu(OH) 2 (5 mol%)
L1 (6 mol%)
D 2O (99.8%), 5 oC
12 h
+
2
(1.6 equiv)
H
NaBO 3
OH
Ph
H D
5ab-D
79% yield, 87.5:12.5 e.r.
>99.4% D incorporation
Scheme S-2 Deuteration of cyclic dienone 4a in D2O
H
O
H
O
H
O
Cu
Cu
Cu
O
H
Cu
O
H
O
H
Fig. S-1 Polymeric µ-hydroxide Cu
O
H
O
O
H
O
Cu
Ph
OH
O
H
B(pin)
HO
Cu
N
N
N
N
tBu
Cu
tBu
OH
Ph
B(pin)
OH
[Cu(OH) 2]
[Cu(OAc) 2]
Fig. S-2 Plausible intermediate structures of Cu(OH)2- and Cu(OAc)2-catalyzed reactions of cyclic dienone 4a
S-2