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19
General Procedure
for the Synthesis of α-Aminonitriles
Trimethylsilyl
cyanide (2, 120 mg, 1.2 mmol) was added dropwise
to a solution of an N-alkoxycabonylamino
sulfone 1 (1 mmol) and InCl3 (22.1
mg, 10 mol%) in CH2Cl2 (5 mL) under
nitrogen. The mixture was stirred, and the reaction was monitored
by TLC. After completion, the reaction was quenched with distilled
H2O (5 mL) and the mixture was extracted with EtOAc (3 ×10
mL). The combined organic portions were washed with H2O
(2 × 10 mL) and sat. aq NH4Cl
solution (2 × 10 mL), dried over anhyd
Na2SO4, and concentrated under vacuum. The
crude product was subjected to column chromatography (silica gel,
hexane-EtOAc = 85:15 to 90:10) to obtain pure
protected α-aminonitrile.
Spectroscopic
Data of some Representative Products
2-(Benzyloxycarbonylamino)-2-(phenyl)acetonitrile
(3a)
White solid; mp 107-109 ˚C.
IR (KBr): 3278, 3031, 1694, 1521, 1451 cm-¹. ¹H
NMR (200 MHz, CDCl3): δ = 7.55-7.24
(10 H, m), 5.80 (1 H, br d, J = 8.7
Hz), 5.37 (1 H, br d, J = 8.7
Hz), 5.12 (2H, s). ¹³C NMR (50 MHz,
CDCl3): δ = 155.2, 135.7, 133.3, 129.9,
129.6, 128.9, 128.7, 128.5, 127.1, 117.6, 68.2, 46.8. MS-FAB: m/z = 267 [M + H]+. ESI-HRMS: m/z calcd for C16H14N2O2Na [M + Na]+: 289.0952;
found: 289.0951.
2-(Benzyloxycarbonylamino)-2-(4-methoxyphenyl)-acetonitrile
(3g)
White solid; mp 113-115 ˚C.
IR (KBr): 3296, 1688, 1612, 1519, 1253 cm-¹. ¹H
NMR (200 MHz, CDCl3): δ = 7.43 (2 H,
d, J = 8.0
Hz), 7.40-7.31 (5 H, m), 6.92 (2 H, d, J = 8.0 Hz),
5.76 (1 H, d, J = 8.0
Hz), 5.22 (1 H, d, J = 8.0
Hz), 5.18 (2 H, s), 3.82 (3 H, s). ¹³C
NMR (50 MHz, CDCl3): δ = 160.7, 155.2,
135.7, 128.8, 128.7, 128.6, 128.5, 125.2, 117.8, 114.9, 68.1, 55.6,
46.3. ESI-MS: m/z = 297 [M + H]+, 319 [M+Na]+.
ESI-HRMS: m/z calcd for C17H16N2O3Na [M + Na]+:
319.1058; found: 319.1069.
2-(Benzyloxycarbonylamino)-2-(3-nitrophenyl)aceto-nitrile
(3j)
White solid; mp 112-114 ˚C.
IR (KBr): 3280, 3057, 1692, 1532 cm-¹. ¹H
NMR (200 MHz, CDCl3): δ = 8.37 (1 H,
t, J = 7.0
Hz), 8.33 (1 H, dd, J = 8.0,
2.0 Hz), 7.83 (1 H, dd, J = 8.0,
2.0 Hz), 7.62 (1 H, t, J = 8.0
Hz), 7.35 (5 H, br s), 5.95 (1 H, br d, J = 8.0
Hz), 5.52 (1 H, d, J = 8.0
Hz), 5.17 (2 H, s). ¹³C NMR (50 MHz,
CDCl3): δ = 155.2, 148.9, 135.6, 135.3,
133.0, 130.7, 128.7, 128.5, 124.7, 122.2, 116.6, 68.5, 46.0. MS-FAB: m/z = 311 [M]+.
ESI-HRMS:
m/z calcd
for C16H13N3O4Na [M + Na]+:
334.0803; found: 334.0820.
2-(Benzyloxycarbonylamino)-2-(2-naphthyl)aceto-nitrile (3l)
White
solid; mp 133-135 ˚C. IR(neat): 3283, 1690, 1517, 1289
cm-¹. ¹H NMR (200
MHz, CDCl3): δ = 7.98 (1 H, d, J = 2.0 Hz),
7.90-7.79 (3 H, m), 7.58-7.45 (3 H, m), 7.38-7.27
(5 H, m), 5.99 (1 H, d, J = 8.0
Hz), 5.39 (1 H, d, J = 8.0 Hz),
5.18 (2 H, s). ¹³C NMR (50 MHz, CDCl3): δ = 155.1, 135.5,
133.5, 133.0, 130.2, 129.6, 128.7, 128.6, 128.3, 128.2, 127.8, 127.3,
127.1, 126.5, 123.9, 117.5, 68.0, 46.8. ESI-MS: m/z = 317 [M + H]+.
ESI-HRMS: m/z calcd for C20H16N2O2Na [M + Na]+:
339.1109; found: 339.1125.
2-(Benzyloxycarbonylamino)-2-(2-furyl)acetonitrile (3m)
Pale
grey solid; mp 104-106 ˚C. IR(neat): 3270, 1694,
1532, 1255 cm-¹. ¹H
NMR (200 MHz, CDCl3): δ = 7.42 (1 H,
d, J = 1.5
Hz), 7.39-7.22 (5 H, m), 6.52 (1 H, d, J = 3.0
Hz), 6.38 (1 H, dd, J = 3.0,
1.5 Hz), 5.89 (1 H, d, J = 8.0
Hz), 5.45 (1 H, d, J = 8.0
Hz), 5.14 (2 H, s). ¹³C NMR
(50 MHz, CDCl3): δ = 154.8, 145.0,
144.1, 135.3, 128.6, 128.5, 128.2, 115.6, 110.9, 109.8, 68.0, 40.5.
ESI-MS: m/z = 257 [M + H]+.
ESI-HRMS: m/z calcd for C14H12N2O3Na [M + Na]+: 279.0745;
found: 279.0742.
2-(Benzyloxycarbonylamino)-3-methylbutyronitrile
(3r)
Colorless oil. IR(neat): 3324, 3035, 1706, 1527,
1266, 1237 cm-¹. ¹H
NMR (200 MHz, CDCl3): δ = 7.35-7.26
(5 H, br s), 5.16 (1 H, br d, J = 8.0
Hz), 5.12 (2 H, s), 4.50 (1 H, t, J = 8.0 Hz),
2.03 (1 H, m), 1.11 (3 H, d, J = 7.0
Hz), 1.07 (3 H, d, J = 7.0
Hz). ¹³C NMR (50 MHz, CDCl3): δ = 155.5,
135.8, 128.8, 128.7, 127.0, 117.9, 67.8, 49.0, 31.8, 18.9, 18.2.
MS-FAB: m/z 233 [M + H]+.
ESI-HRMS: m/z calcd for C13H16N2O2Na [M + Na]+:
255.1109; found: 255.1102.
20a
Banphavichit V.
Chaleawlertumpon S.
Bhanthumnavin W.
Vilaivan T.
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Uematsu Y.
Fujimoto J.
Fukumoto K.
Maruoka K.
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