European Journal of Organic Chemistry
10.1002/ejoc.201800454
FULL PAPER
tert-Butyl-(R)-5-chloro-3-((R)-1-ethoxy-1,4-dioxo-4-
tert-Butyl-(R)-3-((R)-1-ethoxy-1,4-dioxo-4-phenylbutan-2-
yl)-5-methoxy-2-oxoindoline-1-carboxylate (3f): White
phenylbutan-2-yl)-2-oxoindoline-1-carboxylate
(3c):
); 97%
White solid; 91% yield; [α] 2
5= -24.0 (c 0.10, CHCl
solid; 92% yield; [α]
ee; 58:42 dr; HPLC [Chiralpak AD-H, hexane/i-PrOH, 92:8, 1
mL/min, 254 nm, (Isomer A) t = 8.87 min (major), t = 14.1
= 11.0 min (minor) and t
) δ 7.92-7.95 (m,
25= -27.9 (c 0.10, CHCl
); 96% (94%)
D 3
D
3
(95%) ee; 61:39 dr; HPLC [Chiralpak AD-H, hexane/i-PrOH,
9
7.5:2.5, 1 mL/min, 254 nm, (Isomer A) t
R
=
18.1 min
R
R
(
major), t
R
= 35.4 min (minor) and (Isomer B) t
R
= 24.4 min
min (minor) and (Isomer B) t
13.3 min (major)]; H NMR (500 MHz, CDCl
R
R
=
= 38.3 min (major)]; 1H NMR (500 MHz,
1
(minor) and t
R
3
CDCl
3
) δ 7.94-7.97 (m, 2H), 7.78-7.81 (m, 1H), 7.55-7.59 (m, 2H), 7.75 (d, J = 8.85 Hz, 1H), 7.53-7.56 (m, 1H), 7.42-7.46
1
4
3
2
1
1
8
1
1
1
4
H), 7.45-7.48 (m, 2H), 7.33 (s, 1H), 7.28-7.30 (m, 1H), 4.06-
(m, 2H), 6.82-6.89 (m, 2H), 4.06-4.16 (m, 2H), 3.97-4.01 (m,
1H), 3.90 (d, J = 3.10 Hz, 1H), 3.71-3.78 (m, 3H), 3.57-3.62
(m, 1H), 3.48 (dd, J = 18.1 Hz, J = 6.50 Hz, 1H), 2.66 (dd, J
= 17.3 Hz, J = 3.80 Hz, 1H), 1.62-1.65 (m, 9H), 1.11-1.15 (m,
.13 (m, 2H), 3.95-4.01 (m, 1H), 3.87 (d, J = 2.95 Hz, 1H),
.72-3.79 (m, 1H), 3.53 (dd, J = 18.2 Hz, J = 5.65 Hz, 1H),
.79 (dd, J = 17.3 Hz, J = 4.30 Hz, 1H), 1.63-1.64 (m, 9H),
.11-1.13 (m, 3H); 13C NMR (125 MHz, CDCl
) δ 13.79,
3H); 13C NMR (125 MHz, CDCl
) δ 13.80, 13.82, 28.12,
3
3
3.81, 28.09, 36.26, 37.26, 41.54, 42.11, 45.64, 47.09, 61.52, 35.87, 37.01, 41.50, 42.02, 46.18, 47.57, 55.65, 61.34, 61.40,
4.65, 84.93, 116.2, 116.3, 123.8, 124.0, 128.0, 128.1, 128.4, 84.13, 84.36, 109.8, 110.2, 113.4, 113.5, 115.8, 116.0, 127.2,
28.6, 128.7, 128.9, 129.8, 129.9, 133.4, 133.5, 136.4, 136.4, 128.1, 128.5, 128.6, 133.2, 133.3, 133.6, 133.9, 136.5, 136.7,
38.8, 139.1, 148.9, 149.0, 171.2, 172.0, 173.1, 174.2, 197.1, 149.2, 149.3, 156.8, 156.9, 171.4, 172.2, 173.0, 174.7, 197.3,
97.3; HRMS (ESI-TOF) m/z: calcd for C25
H
26ClNO
6
[M+Na]+
197.4; HRMS (ESI-TOF) m/z: calcd for C26H29NO
7
[M+Na]+
490.1842; found 490.2223.
94.1346; found 494.1339.
tert-Butyl-(R)-5-bromo-3-((R)-1-ethoxy-1,4-dioxo-4-
tert-Butyl-(R)-3-((R)-1-ethoxy-1,4-dioxo-4-phenylbutan-2-
yl)-5-methyl-2-oxoindoline-1-carboxylate (3g): White
solid; 90% yield; [α] ); 96% (96%)
25= -27.9 (c 0.10, CHCl
ee; 60:40 dr; HPLC [Chiralpak IA, hexane/i-PrOH, 97:3, 1
mL/min, 254 nm, (Isomer A) t = 18.6 min (major), t = 30.6
= 25.7 min (minor) and t
) δ 7.93-7.95 (m,
phenylbutan-2-yl)-2-oxoindoline-1-carboxylate
(3d):
White solid; 88% yield; [α]
D
25= -24.9 (c 0.10, CHCl
3
); 95%
D
3
(
9
96%) ee; 62:38 dr; HPLC [Chiralpak AD-H, hexane/i-PrOH,
2:8, 1 mL/min, 254 nm, (Isomer A) t = 9.80 min (major),
= 11.6 min (minor)
) δ
R
R
R
t
R
= 14.4 min (minor) and (Isomer B) t
R
min (minor) and (Isomer B) t
33.2 min (major)]; H NMR (500 MHz, CDCl
R
R
=
1
1
and t
R
= 16.2 min (major)]; H NMR (500 MHz, CDCl
3
3
7
7
3
1
1
3
3
1
1
1
.94-7.97 (m, 2H), 7.73-7.76 (m, 1H), 7.56-7.58 (m, 1H),
2H), 7.70 (d, J= 8.65 Hz, 1H), 7.43-7.57 (m, 2H), 7.09-7.12
(m, 2H), 4.07-4.15 (m, 2H), 3.97-4.01 (m, 1H), 3.88 (d, J =
2.95 Hz, 1H), 3.56-3.77 (m, 1H), 3.48 (dd, J = 18.1 Hz, J =
6.55 Hz, 1H), 2.65 (dd, J = 17.3 Hz, J = 3.70 Hz, 1H), 2.32-
2.35 (m, 3H), 1.62-1.65 (m, 9H), 1.11-1.14 (m, 3H); 13C NMR
.43-7.48 (m, 4H), 4.06-4.13 (m, 2H), 3.94-3.99 (m, 1H),
.87 (d, J= 2.95 Hz, 1H), 3.76 (dd, J = 18.4 Hz, J = 8.50 Hz,
H), 3.54 (dd, J = 18.2 Hz, J = 5.55 Hz, 1H), 2.80 (dd, J =
7.3 Hz, J = 4.35 Hz, 1H), 1.62-1.64 (m, 9H), 1.11-1.13 (m,
H); 13C NMR (125 MHz, CDCl
) δ 13.74, 13.82, 28.10,
3
3
(125 MHz, CDCl ) δ 13.81, 13.83, 21.06, 21.09, 28.14, 35.97,
6.27,37.31, 41.58, 42.17, 45.6, 47.02, 61.53, 84.67, 84.96,
16.6, 116.7, 126.6, 126.8, 128.2, 128.4, 128.6, 128.7,
31.4, 131.8, 133.4, 133.5, 136.4, 136.5, 139.4, 148.9,
49.0, 171.2, 171.9, 173.0, 174.1, 197.1, 197.3; HRMS
37.10, 41.54, 42.03, 45.99, 47.38, 61.32, 61.37, 84.17, 84.41,
114.8, 114.9, 124.2, 124.3, 125.0, 125.8, 128.1, 128.5, 128.6,
128.9, 129.3, 133.3, 133.4, 134.0, 134.2, 136.5, 136.6, 137.9,
138.2, 149.2, 171.5, 172.3, 174.0, 174.9, 197.5, 197.6;
(
ESI-TOF) m/z: calcd for C25
H
26BrNO
6
[M+Na]+ 538.0841;
HRMS (ESI-TOF) m/z: calcd for
C
26
H29NO
6
[M+Na]+
found 538.0834.
474.1893; found 474.1857.
tert-Butyl-(R)-3-((R)-1-ethoxy-1,4-dioxo-4-phenylbutan-2-
yl)-5-iodo-2-oxoindoline-1-carboxylate (3e): White solid;
Benzyl-(R)-3-((R)-1-ethoxy-1,4-dioxo-4-phenylbutan-2-
yl)-2-oxoindoline-1-carboxylate (3h): Brown solid; 87%
8
9% yield; [α]
7:43 dr; HPLC [Chiralpak AD-H, hexane/i-PrOH, 92:8, 1
7.23 min (major), t
= 8.19 min (minor) and
= 11.0 min (major)]; H NMR (500 MHz, CDCl ) δ 7.94-
D
25= -21.0 (c 0.10, CHCl
3
); 96% (97%) ee;
yield; [α]
HPLC [Chiralpak AS-H, hexane/i-PrOH, 80:20, 1 mL/min,
254 nm, (Isomer A) t = 12.8 min (minor), t = 17.4 min
= 20.4 min (major) and t = 29.2
) δ 7.89-7.95 (m,
D
25= -12.9 (c 0.10, CHCl
3
); 95% (96%) ee; 64:36 dr;
5
mL/min, 254 nm, (Isomer A) t
R
=
R
=
R
R
9
.44 min (minor) and (Isomer B) t
R
(major) and (Isomer B) t
min (minor)]; H NMR (500 MHz, CDCl
R
R
1
1
t
R
3
3
7
4
3
.98 (m, 2H), 7.56-7.65 (m, 4H), 7.45-7.49 (m, 2H), 4.03-
.13 (m, 2H), 3.93-3.98 (m, 1H), 3.85 (d, J = 3.0 Hz, 1H),
.72-3.81 (m, 1H), 3.54 (dd, J = 5.45 Hz, J= 18.2 Hz), 2.79
3H), 7.49-7.57 (m, 3H), 7.41-7.46 (m, 2H), 7.36-7.40 (m,
2H), 7.29-7.35 (m, 3H), 7.14-7.20 (m, 1H), 5.40-5.50 (m,
2H), 4.19 (d, J = 3.75 Hz, 1H), 3.99-4.11 (m, 3H) , 3.95 (d,
J = 3.15 Hz, 1H), 3.64-3.79 (m, 1H) , 3.49 (dd, J = 6.15 Hz,
J =18.0 Hz, 1H), 2.72 (dd, J = 4.10 Hz, J = 17.2 Hz, 1H),
(dd, J = 4.30 Hz, J =17.3 Hz, 1H), 1.62-1.64 (m, 9H), 1.10-
1
2
8
1
1
.14 (m, 3H); 13C NMR (125 MHz, CDCl
3
) δ 13.79, 13.84,
8.09, 36.22, 37.35, 41.56, 42.18, 45.34, 46.83, 61.52,
4.66, 84.97, 87.71, 87.77, 116.9, 117.1, 128.2, 128.6,
28.7, 128.8, 136.4, 136.5, 137.4, 137.8, 140.1, 140.4,
48.9, 149.0, 171.2, 171.9, 172.9, 173.9, 197.1, 197.4;
1.04-1.08 (m, 3H); 13C NMR (125 MHz, CDCl
3
) δ 13.78,
36.12, 37.05, 41.69, 42.33, 45.77, 47.28, 61.41, 61.44,
68.62, 68.73, 115.1, 115.3, 123.6, 123.7, 124.7, 124.8,
125.2, 126.0, 128.1, 128.2, 128.5, 128.6, 128.7, 128.8,
129.0, 133.3, 133.4, 134.9, 135.0, 136.5, 139.9, 140.2,
150.8, 150.9, 171.3, 172.2, 173.7, 174.5, 197.2, 197.4;
HRMS (ESI-TOF) m/z: calcd for
86.0703; found 586.0717.
C
25
H26INO
6
[M+Na]+
5
6
This article is protected by copyright. All rights reserved.