H
5
M. M. Maturi, A. P o¨ thig, and T. Bach
6
3
4
3
298 K) 8.76 (1H, br s, NH), 7.60 (1H, dd, J 8.2, J 0.8, H-6),
4
J E J 0.6, H-4), 7.05 (1H, dd, J 8.1, J 1.8, H-5), 6.97 (1H, dd,
4
5
6
6
J 1.8, J 0.5, H-7), 1.77 (3H, d, J 0.5, CH ), 1.62 (3H, d, J 0.5,
4
3
7.42 (1H, d, J 0.8, H-4), 7.06 (1H, d, J8.2, H-7), 1.78 (3H, s, CH ),
3
3
CH ). d (CDCl , 63 MHz, 300 K) 174.68 (s, C-2), 143.1 (s,
3
C-7a), 135.7 (s, C-6), 126.0 (d, C-5), 122.4 (d, C-4), 122.4 (s,
C-3a), 111.2 (d, C-7), 67.4 (s, C–O), 64.7 (s, C-3), 21.1
1.65 (3H, s, CH ). d (CDCl ,101 MHz, 300 K) 175.2 (s, C-2),
3
3
C
3
C
3
145.1 (s, C-7a), 127.4 (dq, J 3.7, C-4), 125.0 (s, C-3a), 124.9 (q,
CF
2
1
JCF 35.9, C-5), 124.1 (q, J 282, CF ), 122.1 (dq, J 3.5, C-6),
3
CF
3
CF
(
H] (C H
q, CH ), 18.7 (q, CH ). m/z (HRMS ESI) 224.0473; [M þ
110.6 (d, C-7), 67.8 (s, C-O), 64.8 (s, C-3), 21.4 (q, CH ), 18.7
3
3
3
þ
35
þ
ClNO ) requires 224.0473. m/z (HRMS ESI)
2
(q, CH ). m/z (HRMS ESI) 258.0736; [M þ H] (C H F NO )
1
1
10
3
12 10
3
2
þ
37
2
26.0444; [M þ H] (C H
ClNO ) requires 226.0443.
2
requires 258.0736.
1
1
10
6
rac-4f): Prepared from 7f according to RP 2 on a 1.25 mmol
-Chloro-39,39-diethylspiro[indolin-3,29-oxiran]-2-one
5-Chloro-39,39-dimethylspiro[indolin-3,29-oxiran]-2-one
(rac-4j): Prepared from 7j according to RP 2 on a 1.69 mol scale.
The title compound (119 mg, 532 mmol, 31 %) was obtained as a
(
scale. The title compound (207 mg, 822 mmol, 65 %) was
obtained as a colourless solid. R 0.81 (P/EE ¼ 1 : 1; UV). n
ꢁ
1
colourless solid. R 0.55 (P/EE ¼ 1 : 1; UV). n
(ATR)/cm
3127br (NH), 2966w, 2934w, 1712vs (C¼O), 1688s, 1618m,
1189w, 1126w, 1070w, 903w, 772w. l /nm (CH CN,
F
max
F
max
ꢁ
1
(
ATR)/cm 3128br (NH), 2968w, 2930w, 1708vs (C¼O),
1
1
2
7
619s, 1460m, 1334w, 1220w, 919w, 661w. l /nm (CH CN,
max
3
max
3
ꢁ1
ꢁ1
ꢁ1
ꢁ1
.0 mM) (e/M cm ) 301 (1800), 254 (5520). d (CDCl3,
1.0 mM) (e/M cm ) 312 (1510), 255 (7790). dH (CDCl ,
H
3
3
50 MHz, 300 K) 8.03 (1H, br s, NH), 7.11 (1H, d, J 8.1, H-4),
3 4
400 MHz, 298 K) 8.23 (1H, br s, NH), 7.28 (1H, dd, J 8.4, J 2.1,
3
4
4
.02 (1H, dd, J 8.1, J 1.8, H-5), 6.94 (1H, d, J 1.8, H-7), 2.27
4
3
H-6), 7.16 (1H, d, J 2.1, H-4), 6.87 (1H, d, J 8.4, H-7), 1.76
(3H, s, CH ), 1.62 (3H, s, CH ). d (CDCl , 101 MHz, 300 K)
2
3
2
3
(1H, dq, J 15.0, J 7.4, CHH), 2.07 (1H, dq, J 14.4, J 7.5,
CHH), 1.98 (1H, dq, J 15.0, J 7.4, CHH), 1.78 (1H, dq, J 14.4,
3
J 7.5, CHH), 1.02 (3H, t, J 7.4, CH ), 1.00 (3H, t, J 7.5, CH ).
3
3
C
3
2
3
2
174.7 (s, C-2), 140.6 (s, C-7a), 129.7 (d, C-6), 127.9 (s, C-5),
125.7 (s, 3a), 125.4 (d, C-4), 111.5 (d, C-7), 67.6 (s, C–O), 64.9
(s, C-3), 21.2 (q, CH ), 18.7 (q, CH ). m/z (HRMS ESI)
3
3
3
3
dC (CDCl , 63 MHz, 300 K) 174.9 (s, C-2), 143.0 (s, C-7a),
3
3
3
þ
35
10
1
1
35.5 (s, C-6), 125.8 (d, C-5), 122.5 (s, C-3a), 122.4 (d, C-4),
11.1 (d, C-7), 74.9 (s, C–O), 65.2 (s, C-3), 23.1 (t, CH ), 20.8 (t,
224.0472; [M þ H] (C H ClNO ) requires 224.0473. m/z
þ
11 10 2
1
1
2
37
(HRMS ESI) 226.0443; [M þ H] (C H ClNO ) requires
2
CH ), 9.87 (q, CH ). 9.47 (q, CH ). m/z (HRMS ESI) 252.0785;
2
226.0443.
3
35
3
þ
[
2
M þ H] (C H ClNO ) requires 252.0786. m/z (HRMS ESI)
6-Bromo-39,39-dimethylspiro[indolin-3,29-oxiran]-2-one
(rac-4k): Prepared from 7k according to RP 2 on a 595 mmol
scale. The title compound (160 mg, 595 mmol, .99 %) was
1
3
14
2
þ
37
54.0756; [M þ H] (C H ClNO ) requires 254.0765.
1
3
14
2
5
-Methoxy-39,39-dimethylspiro[indolin-3,29-oxiran]-2-one
(
rac-4g): Prepared from 7g according to RP 2 on a 836 mmol
obtained as a colourless solid. R 0.75 (P/EE ¼ 1 : 1; UV).
F
RT
D
RT
D
scale. The title compound (142 mg, 650 mmol, 78 %) was
obtained as a colourless solid. R 0.64 (P/EE ¼ 1 : 1; UV). n
½aꢃ þ81.0 (c 1.0 in CH Cl , 100 % ee, 4k); ½aꢃ ꢁ79.9 (c
ꢁ
2 2 max
2
2
1
1.0 in CH Cl , 100 % ee, ent-4k). n
(ATR)/cm 3253br
F
max
ꢁ
1
(
ATR)/cm
3276br (NH), 3019w, 2966w, 2931w, 1725s,
(NH), 2935w, 1728vs (C¼O), 1713vs, 1607s, 1479m, 1448w,
ꢁ
max 3
1
1
l
(
6
685vs (C¼O), 1483m, 1437w, 1208w, 1027w, 825w, 755w.
1356w, 1191w, 911w, 688s. l /nm (CH CN, 1.0 mM) (e/M
ꢁ1
ꢁ1
ꢁ1
cm ) 301 (1830), 252 plateau (5540). dH (CDCl , 400 MHz,
3
298 K) 8.20 (1H, br s, NH), 7.19 (1H, dd, J 8.1, J 1.7, H-5),
4
7.11 (1H, d, J 1.7, H-7), 7.04 (1H, d, J 8.1, H-4), 1.75 (3H, s,
CH ), 1.60 (3H, s, CH ). d (CDCl , 101 MHz, 300 K) 174.8
/nm (CH CN, 1.0 mM) (e/M cm ) 323 (1780), 261
max
3
3
4
6814). dH (CDCl , 400 MHz, 300 K) 8.48 (1H, br s, NH),
3
4
3
.87–6.81 (2H, m, H6/H-7), 6.79 (1H, br d, J 2.0, H-4), 3.78
3H, s, OCH ), 1.77 (3H, s, CH ), 1.62 (3H, s, CH ). d (CDCl ,
(
3
3
3
C
3
3
3
C
3
1
1
6
01 MHz, 300 K) 175.4 (s, C-2), 155.6 (s, C-5), 135.5 (s, C-7a),
25.2 (s, C-3a), 114.3 (d, C-4), 112.5 (d, C-6), 111.0 (d, C-7),
7.1 (s, C–O), 65.5 (s, C-3), 56.0 (q, OCH ), 21.0 (q, CH ), 18.8
(s, C-2), 143.2 (s, C-7a), 126.3 (d, C-5), 125.3 (d, C-4), 123.3 (s,
C-3a), 122.9 (s, C-6), 114.0 (d, C-7), 67.4 (s, C–O), 64.8 (s, C-3),
n
21.1 (q, CH ), 18.7 (q, CH ). Chiral HPLC: (AS-H, hexane/
i-
3
3
3
3
þ
ꢁ1
(
q, CH ). m/z (HRMS ESI) 220.0968; [M þ H] (C H NO )
PrOH ¼ 70 : 30, 1 mL min , l 210 nm and 254 nm); t 12.1 min
3
12 13
3
R
þ
requires 220.0968.
-Methyl-39,39-dimethylspiro[indolin-3,29-oxiran]-2-one
rac-4h): Prepared from 7h according to RP 2 on a 561 mmol
(4k), t 24.2min (ent-4k). m/z (HRMS ESI) 267.9968; [M þ H]
R
7
9
5
(C H BrNO ) requires 267.9967. m/z (HRMS ESI) 269.9947;
11 10 2
þ
81
10
(
[M þ H] (C H BrNO ) requires 269.9947.
1
1
2
scale. The title compound (68.8 mg, 343 mmol, 61 %) was
obtained as a colourless solid. R 0.71 (P/EE ¼ 1 : 1; UV). n
F
max
ꢁ
1
3-Acylindolin-2-ones
(ATR)/cm
3308br (NH), 2966w, 2919w, 2850w, 1731s,
1
704vs (C¼O), 1622m, 1487m, 1375w, 1156m, 755w, 710w.
(R)-3-Ethyl-3-propionylindolin-2-one (6b): Prepared from
rac-4b according to RP 4 on a 100 mmol scale. The title
ꢁ1
ꢁ1
l
/nm (CH CN, 1.0 mM) (e/M cm ) 309 (1490), 253
max
3
(6190). dH (CDCl , 250 MHz, 300 K) 8.12 (1H, br s, NH),
compound (19.8 mg, 91.1 mmol, 91 %, 33 % ee) was obtained
3
3
.10 (1H, dd, J 7.9, J 0.8, H-6), 7.00 (1H, br s, H-4), 6.82
4
RT
D
3228br (NH),
7
(
as a colourless solid. R
F
0.58 (P/EA ¼ 1 : 1; UV). ½aꢃ þ16.3 (c
3
1H, d, J 7.9, H-7), 2.33 (3H, s, C5–CH ), 1.76 (3H, s, CH ),
ꢁ1
1.0 in CH Cl , 33 % ee). nmax (ATR)/cm
2 2
3
3
1
1
1
.62 (3H, s, CH ). d (CDCl , 63 MHz, 300 K) 175.2 (s, C-2),
3
39.7 (s, C-7a), 131.9 (s, C-5), 130.5 (d, C-4), 125.9 (d, C-6),
24.0 (d, C-3a), 110.3 (d, C-7), 67.0 (s, C–O), 65.2 (s, C-3), 21.3
2983w, 2929w, 1700vs (C¼O), 1690vs (C¼O), 1610m,
1312m, 1212m, 1197m. d (CDCl , 250 MHz, 300 K) 9.11
(1H, br s, NH), 7.28 (1H, virt. td, JE J 7.6, J 1.6, H-6), 7.14
3
C
H
3
3
3
4
3
4
3
3
4
(q, C5–CH ), 21.1 (q, CH ), 18.8 (q, CH ). m/z (HRMS ESI)
3
(1H, dd, J 7.5, J 1.5, H-4) 7.06 (1H, virt. td, JE J 7.4, J 1.0,
3
3
þ
3 2 3
H-5) 6.98 (1H, d, J 7.7, H-7), 2.55 (1H, dq, J 18.4, J 7.2,
2
04.1019; [M þ H] (C H NO ) requires 204.1019.
1
2
13
2
3
5
-Trifluoromethyl-39,39-dimethylspiro[indolin-3,29-oxiran]-
COCHH), 2.34–2.17 (3H, m, COCHH/C3–CH
2
), 0.95 (3H, t, J
CH ). d (CDCl ,
3
3
), 0.67 (3H, t, J 7.4, C3–CH
2-one (rac-4i): Prepared from 7i according to RP 2 on a 829 mmol
7.2, COCH
CH
2
3
2
3
C
scale. The title compound (213 mg, 829 mmol, .99%) was
obtained as a colourless solid. R 0.75 (P/EE ¼ 1 : 1; UV). n
63 MHz, 300 K) 204.2 (s, CO), 178.0 (s, C-2), 141.8 (s, C-7a),
129.1 (d, C-6), 128.4 (s, C-3a), 124.2 (d, C-5), 123.2 (d, C-4),
F
max
ꢁ
1
(
ATR)/cm 3051br (NH), 2896w, 2864w, 1719vs (C¼O), 1626s,
110.3 (d, C-7), 67.7 (s, C-3), 32.6 (t, COCH
8.21 (q, COCH CH ), 7.75 (q, C3–CH CH
218.1174; [M þ H] (C13 ) requires 218.1176. Chiral
2
), 26.8 (t, C3–CH
). m/z (HRMS ESI)
3
2
),
1
332m, 1298m, 1105vs, 1056m, 749w. l /nm (CH CN, 1.0 mM)
2
3
þ
2
max
3
ꢁ1
ꢁ1
(
e/M cm ) 297 (1540), 254 (7500). dH (CDCl , 400 MHz,
H15NO
2
3