β-Keto esters from ketones and ethyl chloroformate: a rapid, general ...
Synthesis of Diverse β-Quaternary Ketones via … of Diverse β-Quaternary Ketones via...
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Holder et al. S1 Supporting Information Synthesis of Diverse β -Quaternary Ketones via Palladium- Catalyzed Asymmetric Conjugate Addition of Arylboronic Acids to Cyclic Enones Jeffrey C. Holder, Emmett D. Goodman, Kotaro Kikushima, Michele Gatti, Alexander N. Marziale, and Brian M. Stoltz
Transcript of Synthesis of Diverse β-Quaternary Ketones via … of Diverse β-Quaternary Ketones via...
Holder et al.
S1
Supporting Information
Synthesis of Diverse β-Quaternary Ketones via Palladium-Catalyzed Asymmetric Conjugate Addition of Arylboronic
Acids to Cyclic Enones
Jeffrey C. Holder, Emmett D. Goodman, Kotaro Kikushima, Michele Gatti, Alexander N. Marziale, and Brian M. Stoltz
Holder et al.
S2
Table of Contents
NMR spectra of new compounds (1H, 13C) S3 Table S1. SFC data S27
Holder et al.
S3
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 64
b
Holder et al.
S4
13C
NM
R (1
26 M
Hz,
CD
Cl 3
) of c
ompo
und 64
b
Holder et al.
S5
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 64
c
Holder et al.
S6
13C
NM
R (1
26 M
Hz,
CD
Cl 3
) of c
ompo
und 64
c
Holder et al.
S7
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 64
d
Holder et al.
S8
13C
NM
R (1
26 M
Hz,
CD
Cl 3
) of c
ompo
und 64
d
Holder et al.
S9
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 64
e
Holder et al.
S10
13C
NM
R (1
26 M
Hz,
CD
Cl 3
) of c
ompo
und 64
e
Holder et al.
S11
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 64
f
Holder et al.
S12
13C
NM
R (1
26 M
Hz,
CD
Cl 3
) of c
ompo
und 64
f
Holder et al.
S13
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 64
g
Holder et al.
S14
13C
NM
R (1
26 M
Hz,
CD
Cl 3
) of c
ompo
und 64
g
Holder et al.
S15
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 66
a
Holder et al.
S16
13C
NM
R (1
26 M
Hz,
CD
Cl 3
) of c
ompo
und 66
a
Holder et al.
S17
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 66
b
Holder et al.
S18
13C
NM
R (1
26 M
Hz,
CD
Cl 3
) of c
ompo
und 66
b
Holder et al.
S19
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 66
c
Holder et al.
S20
13C
NM
R (1
26 M
Hz,
CD
Cl 3
) of c
ompo
und 66
c
Holder et al.
S21
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 66
e
Holder et al.
S22
13C
NM
R (1
26 M
Hz,
CD
Cl 3
) of c
ompo
und 66
e
Holder et al.
S23
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 66
f
Holder et al.
S24
13C
NM
R (1
26 M
Hz,
CD
Cl 3
) of c
ompo
und 66
f
Holder et al.
S25
1 H N
MR
(500
MH
z, C
DC
l 3) o
f com
poun
d 66
g
Holder et al.
S26
13C
NM
R (1
26 M
Hz,
CD
Cl 3
) of c
ompo
und 66
g
Holder et al.
S27
Table S1. SFC data and separation conditions
entry productretention time
of majorisomer (min)
% eeretention time
of minorisomer (min)
HPLCconditions
1
2
4
5
6
7
ChiralcelOJ-H15% MeOH/CO2isocratic 5 mL/min
1.64 1.43 96
3
ChiralcelOB-H3% MeOH/CO2isocratic 3 mL/min
5.53 4.48 90
ChiralcelOB-H3% MeOH/CO2isocratic 3 mL/min
ChiralpakAD-H5% MeOH/CO2isocratic 3 mL/min
4.28 3.80 92
5.53 4.83 91
ChiralpakAD-H3% MeOH/CO2isocratic 3 mL/min
7.98 8.97 93
ChiralpakAD-H3% MeOH/CO2isocratic 3 mL/min
6.32 7.96 92
ChiralpakAD-H3% MeOH/CO2isocratic 3 mL/min
4.52 5.02 90
O
O
Cl
O
O
F
O
O
NH(COCF3)O
O
O
O
O
O
O
O
F
Holder et al.
S28
entry productretention time
of majorisomer (min)
% eeretention time
of minorisomer (min)
HPLCconditions
8
10
12
13
14
15
ChiralcelOJ-H1% IPA/Hexanesisocratic 1 mL/min
15.3 19.6 92
11
ChiralcelOJ-H1% IPA/Hexanesisocratic 1 mL/min
15.2 17.1 87
ChiralcelOJ-H0.5% IPA/Hexanesisocratic 1 mL/min
ChiralcelOJ-H1% IPA/Hexanesisocratic 1 mL/min
25.9 34.4 85
29.5 37.1 69
ChiralpakAD-H5% IPA/Hexanesisocratic 1 mL/min
37.9 35.3 74
ChiralpakAD-H5% IPA/Hexanesisocratic 1 mL/min
30.4 29.5 96
ChiralcelOJ-H0.5% IPA/Hexanesisocratic 1 mL/min
16.6 24.9 82
O
NH
O
CF3
O
NH
O
O Ph
NH
O
O
O
NH
O
CF3
O
O
NH
O
CF3
O
HN
O
CF3
O
HN
O
CF3
