10.1002/zaac.201800109
Zeitschrift für anorganische und allgemeine Chemie
ARTICLE
Synthesis of Zr3(L2)3(NMe2)6 (2): A solution of ligand HL1 (0.092 g, 1.0
mmol) in THF (2 mL) was added to Zr(NMe2)4 solution (0.267 g, 1.0 mmol)
in THF (2 mL) carefully at -35 oC. The reaction mixture was stirred at room
temperature overnight after which time volatiles were removed under
reduced pressure to get a yellow solid. Yield: 0.244 g (78%). The yellow
crystals were obtained by recrystallizing in toluene. 1H NMR (600 MHz,
CDCl3): δ 7.73 (s, 1H), 7.24 (s, 1H), 7.00-6.96 (d, J = 28.2 Hz, 2H), 6.54-
6.50 (dd, J = 19.8, 3.6 Hz, 2H), 6.41 (d, J = 3.6 Hz, 1H), 6.24-6.21 (d, J =
18.6 Hz, 2H), 3.50-3.43 (m, 6H), 3.38 (s, 6H), 3.33 (s, 9H), 3.25 (s, 9H),
3.09 (s, 12H), 3.00 (s, 6H), 2.62 (s, 3H), 2.39 (s, 3H). 13C NMR (150 MHz,
CDCl3): δ 169.3, 168.7, 164.8, 136.8, 135.4, 135.1, 132.9, 131.9, 114.8,
111.7, 110.9, 110.5, 109.6, 48.3, 45.4, 45.1, 44.9, 43.8, 43.3, 41.0, 39.8,
38.7. Elemental analysis calcd (%): C 42.00; H 6.73; N 22.27 %; found: C
42.65; H 6.69; N 22.12 %.
4e was afforded from 3e (81 mg, 0.5 mmol) as a light yellow oil in 92%
yield (75 mg). 1H NMR (400 MHz, CDCl3) δ 7.29-7.27 (d, J =7.2 Hz, 2H),
7.24-7.19 (m, 3H), 4.33(s, 1H), 3.53-3.45 (m, 2H), 3.40-3.33 (t, J = 8.2 Hz,
1H), 2.91-2.87 (t, J = 5.8 Hz, 1H), 2.08-2.01 (m, 1H), 1.87-1.80 (m, 1H),
1.26-1.25(d, J = 6.4 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 147.9, 147.2,
128.5, 127.2, 126.2, 58.1, 57.4, 53.3, 47.2, 22.5.
Acknowledgements
The authors appreciate the financial support from National Natural
Science Foundation of China (2127216 and 21772140), and A Project
Funded by the Priority Academic Program Development of Jiangsu
Higher Education Institution.
General procedure for hydroamination reactions
Keywords: hydroamination; zirconium; catalysis; aminoalkenes
The reactions were carried out in a glovebox filled with nitrogen. A solution
of complex 2 (24 mg, 0.025 mmol) in PhCl (2 mL) and 3 was added
subsequently. The resulting solution was stirred at the desired temperature
for the desired time. After reaction, the solvent was removed under vacuo.
Column chromatography of the residue on silica gel gave a pure product.
Notes and references
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2.62 (t, J = 17.1 Hz, 2H), 2.62-2.57 (m, 1H), 1.77-1.75 (d, J = 17.1 Hz, 1H),
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(t, J = 29.7 Hz, 1H), 1.56-1.52 (d, J = 30.6 Hz, 2H), 1.38-1.33 (dd, J = 30.6,
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2-Methyl-indoline (4d)
4d was afforded from 3d (67 mg, 0.5 mmol) as a light yellow oil in 93%
yield (62 mg). 1H NMR (500 MHz, CDCl3) δ 7.05-7.03 (d, J =9.0 Hz, 1H),
7.00-6.96 (t, J =9.5 Hz, 1H), 6.68-6.64 (t, J = 9.3 Hz, 1H), 6.56-6.54 (d, J
= 10.0 Hz, 1H), 3.97-3.89 (m, 1H), 3.66 (s, 1H), 3.13-3.07 (dd, J = 19.0,
10.5 Hz, 1H), 2.62-2.56 (q, J = 9.8 Hz, 1H), 1.25-1.23 (d, J = 8.0 Hz, 3H).
13C NMR (125 MHz, CDCl3) δ 151.1, 129.0, 127.3, 124.8, 118.6, 109.2,
55.3, 37.9, 22.4.
2-Methyl-4-phenyl-pyrrolidine (4e)
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