The Journal of Organic Chemistry
Page 18 of 27
phenyl–1,2,3,4-tetrahydroisoquinoline (8a)39, yellow oil, 57.7 mg, 86%; 1–(1–Nitroethyl)–2–phenyl–1,2,3,4-
tetrahydroisoquinoline (8b)39, yellow oil, 62.8 mg, 89%; 1–(1–Nitropropyl)–2–phenyl–1,2,3,4-tetrahydroisoquinoline (8c)39,
yellow oil, 62.8 mg, 83%; 1–(Nitromethyl)–2–(m–tolyl)–1,2,3,4-tetrahydroisoquinoline (8d)40, yellow oil, 51.5 mg, 73%; 1–(1–
Nitroethyl)–2–(m–tolyl)–1,2,3,4-tetrahydroisoquinoline (8e)40, yellow oil, 49.6 mg, 67%; 1–(Nitromethyl)–2–(p-tolyl)–1,2,3,4-
tetrahydroisoquinoline (8f)39, yellow oil, 60.7 mg, 86%; 1–(Nitromethyl)–2–(p-tolyl)–1,2,3,4-tetrahydroisoquinoline (8g)39,
yellow oil, 63.7 mg, 86%; 2–(4-Methoxyphenyl)–1–(nitromethyl)–1,2,3,4-tetrahydroisoquinoline (8h)39, yellow solid, 54.4 mg,
73%; 2–(4-Methoxyphenyl)–1–(1–nitroethyl)–1,2,3,4-tetrahydroisoquinoline (8i)40, yellow solid, 57.8 mg, 74%; 2–(4-
Chlorophenyl)–1–(nitromethyl)–1,2,3,4-tetrahydroisoquinoline (8j)39, yellow solid, 62.8 mg, 83%; 2–(4-Chlorophenyl)–1–(1–
nitroethyl)–1,2,3,4-tetrahydroisoquinoline (8k)41, yellow solid, 64.1 mg, 81%; 2–(4-Bromophenyl)–1–(nitromethyl)–1,2,3,4-
tetrahydroisoquinoline (8l)39, yellow solid, 73.8 mg, 85%; 2–(4-Bromophenyl)–1–(1–nitroethyl)–1,2,3,4-tetrahydroisoquinoline
(8m)39, yellow solid, 65.0 mg, 72%; 2–(3-Methoxyphenyl)–1–(1–nitroethyl)–1,2,3,4-tetrahydroisoquinoline (8n)42, yellow oil,
58.2 mg, 78%; 2–(2–Methoxyphenyl)–1–(nitromethyl)–1,2,3,4-tetrahydroisoquinoline (8o)39, yellow oil, 27.6 mg, 37%; 6,7-
Dimethoxy–1–(nitromethyl)–2–phenyl–1,2,3,4-tetrahydroisoquinoline (8p)39, yellow oil, 63.2 mg, 77%; Dimethyl 2–(2–phenyl–
1,2,3,4-tetrahydroisoquinolin–1–yl)malonate (9a)39, colorless oil, 76.4 mg, 90%; Diethyl 2–(2–phenyl–1,2,3,4-
tetrahydroisoquinolin–1–yl)malonate (9b)43, colorless oil, 75.3 mg, 82%; 1–(1H–Indol–3-yl)–2–phenyl–1,2,3,4-
tetrahydroisoquinoline (9c)41, yellow solid, 51.9 mg; 1–(5-Methyl–1H–indol–3-yl)–2–phenyl–1,2,3,4-tetrahydroisoquinoline
(9d)44, yellow solid, 53.3 mg, 63%; 1–(1–Methyl–1H–indol–3-yl)–2–phenyl–1,2,3,4-tetrahydroisoquinoline (9e)41, yellow solid,
35.5 mg, 42%; Dimethyl (2–phenyl–1,2,3,4-tetrahydroisoquinolin–1–yl)phosphonate (9f)43, colorless oil, 49.2 mg, 62%; Diethyl
(2–phenyl–1,2,3,4-tetrahydroisoquinolin–1–yl)phosphonate (9g)19b, colorless oil, 52.7 mg, 61%; Diisopropyl (2–phenyl–1,2,3,4-
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tetrahydroisoquinolin–1–yl)phosphonate (9h)19b
,
colorless oil, 53.2 mg, 57%; 1–Phenyl–2–(2–phenyl–1,2,3,4-
tetrahydroisoquinolin–1–yl)ethanone (9i)19b, colorless oil, 51.6 mg, 63%.
1
9–Methyl–1–(nitromethyl)–2–phenyl–2,3,4,9–tetrahydro-1H–pyrido[3,4-b]indole (8q): yellow oil, 54.0 mg, 67% yield. H
NMR (400 MHz, CDCl3) δ 7.49 (d, J = 7.9 Hz, 1H), 7.32 – 7.19 (m, 4H), 7.14 – 7.10 (m, 1H), 7.00 (d, J = 7.9 Hz, 2H), 6.86 (t, J =
7.3 Hz, 1H), 5.61 (dd, J = 10.2, 3.3 Hz, 1H), 4.92 (dd, J = 12.5, 10.3 Hz, 1H), 4.65 (dd, J = 12.5, 3.4 Hz, 1H), 3.97 (dd, J = 14.7, 5.6
Hz, 1H), 3.75 (s, 3H), 3.65 –3.62 (m, 1H), 3.03 – 2.98 (m, 1H), 2.69 (dd, J = 15.9, 3.9 Hz, 1H). 13C {1H} NMR (101 MHz, CDCl3) δ
149.6, 137.6, 130.1, 129.4, 126.6, 122.6, 121.0, 119.7, 118.7, 118.1, 110.8, 109.2, 54.9, 42.1, 29.9, 18.8. IR (KBr, cm-1): 3057, 2942,
1601, 1557, 747. HRMS (ESI-Orbitrap) m/z: [M + H]+ Calcd for C19H20N3O2 322.1550; Found 322.1548.
Kinetic isotope effect studies for amine oxidation. Kinetic isotope effect studies for amine oxidation. (a) Primary amine: To
a solution of o-Q1 (7.76 mg, 0.04 mmol) and 1,3,5-trimethoxybenzene (11.2 mg, 0.06 mmol) in 1 mL of CD3CN in a NMR tube was
added 1-phenylethanamine (48.4 mg, 0.4 mmol) or α-d-1-phenylethanamine (48.8 mg, 0.4 mmol). The NMR tube was flushed with
1
O2. The reaction was monitored by H NMR analysis for 0.5 h (<10% conversion). The initial rates of varied concentration of 1-
phenylethanamine 1a or d-1a (0.25 mol/L, 0.33 mol/L, 0.40 mol/L, 0.56 mol/L, 0.60 mol/L) were measured, respectively. The rate
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