Full Paper
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H, ArH), 3.49 (s, 1 H, CH), 1.77 (br. s, 2 H, NH2), 1.19 [s, 9 H, (CH3)3]
ppm. 13C NMR (125 MHz, CDCl3): δ = 172.09, 132.23, 131.56, 128.52,
128.07, 127.30, 125.82, 125.81, 125.49, 125.47, 124.85, 118.94,
117.05, 65. 31, 34.66, 27.14 ppm. MS (EI): m/z = 306 [M + H]+. HRMS
(EI): calcd. for C20H22N2O [M + H]+ 306.1732, found 306.1728.
(S)-2-Amino-N-(anthracen-1-yl)-2-phenylethanamide (3j): Brown
crystals (EtOAc), 57 % yield. M.p. 52–53 °C. [α]2D2 = –11.50 (c = 2.00,
EtOH). IR (neat): ν = 1685, 1509, 868, 727, 696 cm–1 1H NMR
.
˜
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(500 MHz, CDCl3): δ = 10.24 (br. s, 1 H, NH), 8.41 (s, 1 H, ArH), 8.32
(s, 1 H, ArH), 8.19–8.17 (d, J = 7.16 Hz, 1 H, ArH), 7.98–7.97 (m, 2 H,
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4.83 (s, 1 H, CH), 2.12 (br. s, 2 H, CH) ppm. 13C NMR (125 MHz,
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128.50, 128.44, 128.09, 127.38, 127.16, 125.90, 125.48, 125.41,
125.27, 118.83, 117.36, 60.94 ppm. MS (EI): m/z = 326 [M + H]+.
HRMS (EI): calcd. for C22H18N2O [M + H]+ 326.1419, found 326.1411.
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(3k):
Brown crystals (EtOAc), 60 % yield. M.p. 43–45 °C. [α]2D0 = +19.00
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˜
1
727, 699 cm–1. H NMR (500 MHz, CDCl3): δ = 10.32 (br. s, 1 H, NH),
8.43 (s, 1 H, ArH), 8.27–8.24 (m, 2 H, ArH), 8.00–7.97 (m, 2 H, ArH),
7.82–7.80 (d, J = 8.59 Hz, 1 H, ArH), 7.49–7.46 (m, 3 H, ArH), 7.37–
7.27 (m, 5 H, ArH), 3.97–3.95 (m, 1 H, CH), 3.48–3.45 (dd, J = 14.03,
4.01 Hz, 1 H, CH2), 3.02–2.98 (dd, J = 13.75, 9.16 Hz, 1 H, CH2), 2.02
(br. H, 2 H, NH2) ppm. 13C NMR (125 MHz, CDCl3): δ = 172.78, 172.78,
137.73, 132.24, 132.17, 131.64, 131.58, 129.58, 129.04, 128.53,
128.10, 127.34, 127.19, 125.87, 125.85, 125.48, 125.16, 118.98,
117.24, 57.32, 40.95 ppm. MS (EI): m/z = 340 [M + H]+. HRMS (EI):
calcd. for C23H20N2O [M + H]+ 340.1576, found 340.1583.
General Procedure for the Enantioselective Aldol Reaction of
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Isatins with Ketones: To
a stirred solution of catalyst 3i
(0.015 mmol) in dry THF (2 mL) were added ketone (2 mmol) and
isatin (0.1 mmol) at room temperature. The reaction mixture was
stirred at this temperature and monitored by TLC until the reaction
was completed. Then, THF was removed under reduced pressure.
The concentrated reaction mixture was purified by flash column
chromatography on silica gel (n-hexane/EtOAc = 5:1 to 1:1) to give
the corresponding product.
Acknowledgments
This research was partially supported by the Adaptable & Seam-
less Technology Transfer Program through Targetdriven R&D
from the Japan Science and Technology Agency, JST
(AS231Z01382G and AS221Z01186D), the Northern Advance-
ment Center for Science & Technology and the Muroran Insti-
tute of Technology.
Keywords: Amino amide · Organocatalysis · Aldol
reactions · Isatin · 3-Hydroxy-2-oxindole · Enantioselectivity
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