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1H), 5.92 (m, br, 1H), 5.50 (m, 1H), 5.07 (d, br, J ¼ 16.6 Hz, 1H),
5.01 (d, br, J ¼ 9.8 Hz, 1H), 4.89 (d, J ¼ 15.6 Hz, 1H), 4.82 (d, J ¼
15.6 Hz, 1H), 3.35–2.84 (m, br, 1H), 2.69 (dd, J ¼ 13.7 and 6.8 Hz,
1H), 2.60 (dd, J ¼ 13.7 and 8.8 Hz, 1H), 1.32 (s, 9H). 13C NMR (100
MHz, CDCl3) d 177.3, 156.1, 144.4, 135.1, 134.9, 130.3, 128.9 (2C),
127.8, 127.1 (2C), 126.3, 126.2, 122.5, 120.5, 109.7, 80.6, 68.5, 43.9,
39.6, 28.1 (3C). HRMS (ESI) m/z: 450.1560 [M + Na]+; calcd for
tert-Butyl 2-(3-allyl-1-methyl-2-oxoindolin-3-yl)hydrazinecarbox-
ylate (5b). Prepared according to TP-B starting from compound 4b,
and puried by FC (hexane : ethyl acetate 7 : 3). Yellow foam (82%
yield). 1H NMR (300 MHz, CDCl3) d 7.45 (d, J ¼ 7.8 Hz, 1H), 7.29 (t,
J ¼ 7.8 Hz, 1H), 7.07 (t, J ¼ 7.8 Hz, 1H), 6.80 (d, J ¼ 7.8 Hz, 1H), 5.98
(m, br, 1H), 5.48 (m, 1H), 5.08–4.94 (m, 2H), 3.18 (s, 3H), 3.18–2.77
(m, br, 1H), 2.67 (dd, J ¼ 15.6 and 6.8 Hz, 1H), 2.55 (dd, J ¼ 15.6
and 8.8 Hz, 1H), 1.31 (s, 9H). 13C NMR (100 MHz, CDCl3) d 177.3,
156.1, 143.9, 130.6, 129.2, 127.7, 125.2, 122.5, 119.8, 107.9, 80.3,
68.6, 39.5, 28.1 (3C), 26.1. HRMS (ESI) m/z: 340.1636 [M + Na]+;
+
C23H26ClN3NaO3 , 450.1555.
tert-Butyl 2-(3-allyl-1-benzyl-2-oxo-7-(triuoromethyl)indolin
-3-yl)hydrazinecarboxylate (5g). Prepared according to TP-B
starting from compound 4g, and puried by FC (hex-
ane : ethyl acetate 7 : 3). Yellow foam (75% yield). 1H NMR (300
MHz, CDCl3) d 7.74 (d, br, J ¼ 6.9 Hz, 1H), 7.56 (d, br, J ¼ 7.9 Hz,
1H), 7.33–7.07 (m, 6H), 5.91 (m, br, 1H), 5.48 (m, 1H), 5.20 (d, J
¼ 16.6 Hz, 1H), 5.13 (d, J ¼ 16.6 Hz, 1H), 5.06 (d, br, J ¼ 17.6 Hz,
1H), 5.05 (d, br, J ¼ 10.8 Hz, 1H), 3.34 (m, br, 1H), 2.74–2.56 (m,
2H), 1.32 (s, 9H). 13C NMR (100 MHz, CDCl3) d 178.8, 156.0,
141.5, 136.3, 130.9, 129.8, 129.1, 128.3 (2C), 127.5 (q, J ¼ 5.9 Hz),
126.9, 125.8 (2C), 123.3 (q, J ¼ 271.3 Hz), 122.2, 120.8, 112.8 (q, J
¼ 33.9 Hz), 80.7, 67.0, 45.7, 40.0, 28.1 (3C). HRMS (ESI) m/z:
+
calcd for C17H23N3NaO3 , 340.1632.
(E)-tert-Butyl 2-(3-allyl-1-(3-(3,4-dichlorophenyl)allyl)-2-oxoin-
dolin-3-yl)hydrazinecarboxylate (5c). Prepared according to TP-B
starting from compound 4c, and puried by FC (hexane : ethyl
acetate 1 : 1). Dark yellow foam (93% yield). 1H NMR (300 MHz,
CDCl3) d 7.47 (d, br, J ¼ 7.8 Hz, 1H), 7.42–7.19 (m, 3H), 7.17–7.03
(m, 2H), 6.79 (d, br, J ¼ 7.8 Hz, 1H), 6.41 (d, br, J ¼ 15.6 Hz, 1H),
6.16 (dt, br, J ¼ 15.6 and 4.9 Hz, 1H), 5.98 (m, br, 1H), 5.50 (m, br,
1H), 5.07 (d, J ¼ 17.6 Hz, 1H), 5.01 (d, J ¼ 10.8 Hz, 1H), 5.46 (d, br,
J ¼ 4.9 Hz, 2H), 2.81–2.50 (m, br, 1H), 2.71 (dd, J ¼ 13.7 and
484.1824 [M + Na]+; calcd for C24H26F3N3NaO3 , 484.1818.
+
6.8 Hz, 1H), 2.60 (dd, J ¼ 13.7 and 8.8 Hz, 1H), 1.30 (s, 9H). 13
C
tert-Butyl 2-(3-allyl-1-benzyl-5-nitro-2-oxoindolin-3-yl)hydrazi-
necarboxylate (5h). Prepared according to TP-B starting from
compound 4h, and puried by FC (hexane : ethyl acetate 7 : 3).
Yellow foam (71% yield). 1H NMR (300 MHz, CDCl3) d 8.32 (m, br,
1H), 8.13 (d, br, J ¼ 8.7 Hz, 1H), 7.36–7.17 (m, 5H), 6.71 (d, J ¼
8.7 Hz, 1H), 6.00 (m, 1H), 5.49 (m, 1H), 5.15–5.00 (m, 2H), 4.97 (d,
J ¼ 15.6 Hz, 1H), 4.91 (d, J ¼ 15.6 Hz, 1H), 3.54–2.87 (m, br, 1H),
2.75 (dd, J ¼ 13.0 and 5.8 Hz, 1H), 2.56 (dd, J ¼ 13.0 and 7.8 Hz,
1H), 1.31 (s, 9H). 13C NMR (100 MHz, CDCl3) d 177.4, 156.4, 148.9,
143.4, 134.5, 129.6, 129.1, 129.0 (2C), 127.2 (2C), 126.2, 121.2,
121.0, 120.0, 108.8, 81.3, 68.7, 44.2, 39.6, 28.0 (3C). HRMS (ESI) m/
NMR (100 MHz, CDCl3) d 177.0, 156.2, 143.0, 136.4, 132.7, 131.5,
130.7, 130.4, 129.9, 129.3, 128.2, 127.8, 125.6, 125.4, 124.9, 122.7,
120.1, 108.7, 80.5, 68.6, 41.5, 39.7, 28.1 (3C). HRMS (ESI) m/z:
+
510.1028 [M + Na]+; calcd for C25H27Cl2N3NaO3 , 510.1322.
tert-Butyl 2-(3-allyl-1-benzyl-5-methyl-2-oxoindolin-3-yl)hydrazi-
necarboxylate (5d). Prepared according to TP-B starting from
compound 4d, and puried by FC (hexane : ethyl acetate 7 : 3).
1
Yellow foam (98% yield). H NMR (300 MHz, CDCl3) d 7.33–7.20
(m, 6H), 6.95 (d, br, J ¼ 7.8 Hz, 1H), 6.53 (d, br, J ¼ 7.8 Hz, 1H),
5.98 (m, br, 1H), 5.50 (m, 1H), 5.08 (d, br, J ¼ 17.6 Hz, 1H), 4.99 (d,
br, J ¼ 10.7 Hz, 1H), 4.92 (d, br, J ¼ 15.6 Hz, 1H), 4.81 (d, br, J ¼
15.6 Hz, 1H), 3.72 (m, br, 1H), 2.71 (dd, J ¼ 12.7 and 5.8 Hz, 1H),
2.62 (dd, J ¼ 12.7 and 8.8 Hz, 1H), 2.29 (s, 3H), 1.33 (s, 9H). 13C
NMR (100 MHz, CDCl3) d 173.3, 156.0, 140.8, 135.7, 132.0, 130.8,
129.4, 128.7 (2C), 127.8, 127.5, 127.2 (2C), 125.9, 120.0, 108.9, 80.5,
68.6, 43.8, 39.6, 28.1 (3C), 21.1. HRMS (ESI) m/z: 430.2096 [M +
+
z: 461.1791 [M + Na]+; calcd for C23H26N4NaO5 , 461.1795.
tert-Butyl 2-(3-allyl-1-benzyl-5-methoxy-2-oxoindolin-3-yl)hydraz-
inecarboxylate (5i). Prepared according to TP-B starting from
compound 4i, and puried by FC (hexane : ethyl acetate 7 : 3).
Yellow foam (15% yield). 1H NMR (300 MHz, CDCl3) d 7.34–7.20
(m, 5H), 7.09 (d, br, J ¼ 2.9 Hz, 1H), 6.69 (dd, J ¼ 8.7 and 2.9 Hz,
1H), 6.52 (d, J ¼ 8.7 Hz, 1H), 6.00 (m, br, 1H), 5.51 (m, 1H), 5.08
(d, br, J ¼ 17.6 Hz, 1H), 5.00 (d, br, J ¼ 11.7 Hz, 1H), 4.91 (d, J ¼
15.6 Hz, 1H), 4.82 (d, J ¼ 15.6 Hz, 1H), 3.75 (s, 3H), 2.71 (dd, J ¼
12.7 and 5.8 Hz, 1H), 2.62 (dd, J ¼ 12.7 and 7.8 Hz, 1H), 2.52 (m,
br, 1H), 1.32 (s, 9H). 13C NMR (100 MHz, CDCl3) d 177.8, 156.7
(2C), 137.1, 136.3, 131.3, 129.7, 129.4 (2C), 128.2, 127.9 (2C),
120.8, 114.8 (br), 112.8 (br), 110.2, 81.1, 69.6, 56.5, 44.5, 40.3,
28.8 (3C). HRMS (ESI) m/z: 446.2056 [M + Na]+; calcd for
+
Na]+; calcd for C24H29N3NaO3 , 430.2101.
tert-Butyl 2-(3-allyl-1-benzyl-5-bromo-2-oxoindolin-3-yl)hydrazin-
ecarboxylate (5e). Prepared according to TP-B starting from
compound 4e, and puried by FC (hexane : ethyl acetate 7 : 3).
Yellow foam (82% yield). 1H NMR (300 MHz, CDCl3) d 7.57 (d, J
¼ 1.8 Hz, 1H), 7.35–7.17 (m, 6H), 6.51 (d, J ¼ 7.8 Hz, 1H), 5.91
(m, br, 1H), 5.50 (m, 1H), 5.10 (d, br, J ¼ 16.6 Hz, 1H), 5.03 (d, br,
J ¼ 9.8 Hz, 1H), 4.91(d, br, J ¼ 15.0 Hz, 1H), 4.83 (d, br, J ¼
15.0 Hz, 1H), 3.04–2.71 (m, br, 1H), 2.69 (dd, J ¼ 13.7 and 6.8 Hz,
1H), 2.61 (dd, J ¼ 13.7 and 8.8 Hz, 1H), 1.34 (s, 9H). 13C NMR
(100 MHz, CDCl3) d 176.8, 156.2, 142.3, 135.1, 131.9, 130.2,
130.1, 128.8 (2C), 128.5, 127.7, 127.1 (2C), 120.5, 115.3, 110.6,
80.6, 69,1, 43.9, 39.6, 28.1 (3C). HRMS (ESI) m/z: 494.1055 [M +
C
24H29N3NaO4+, 446.2050.
(3S*,50S*)-tert-Butyl 50-([1,10-biphenyl]-4-ylmethyl)-1-benzyl-2-
oxospiro[indoline-3,30-pyrazolidine]-10-carboxylate (6a) and (3S*
,50R*)-tert-butyl 50-([1,10-biphenyl]-4-ylmethyl)-1-benzyl-2-oxospiro
[indoline-3,30-pyrazolidine]-10-carboxylate (6a0). Prepared accord-
ing to TP-C starting from compound 5a and p-Br-biphenyl, and
puried by FC (hexane : ethyl acetate 7 : 3). Yellow foam (98%
yield, separated diastereoisomers, 1 : 1 dr). Diastereoisomer 6a.
1H NMR (400 MHz, CDCl3) d 7.65–7.57 (m, 4H), 7.48 (t, br, J ¼
7.7 Hz, 2H), 7.44–7.22 (m, 9H), 7.16 (t, br, J ¼ 7.8 Hz, 1H), 6.93 (t,
br, J ¼ 7.8 Hz, 1H), 6.85 (m, br, 1H), 6.65 (d, br, J ¼ 7.8 Hz, 1H),
Na]+; calcd for C23H26BrN3NaO3 , 494.1050.
+
tert-Butyl 2-(3-allyl-1-benzyl-6-chloro-2-oxoindolin-3-yl)hydra-
zinecarboxylate (5f). Prepared according to TP-B starting from
compound 4f, and puried by FC (hexane : ethyl acetate from
8 : 2 to 4 : 6). Dark yellow foam (25% yield). 1H NMR (300 MHz,
CDCl3) d 7.42–7.20 (m, 6H), 7.01 (d, br, J ¼ 7.8 Hz, 1H), 6.33 (m,
37794 | RSC Adv., 2019, 9, 37788–37800
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