COMMUNICATIONS
Amines were distilled from CaH2. Alkynes were degassed, flushed with
argon, and stored over molecular sieves (4 ä). All experiments were
carried out under an argon atmosphere.
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Catalysts 1 and 2 were synthesized according to a literature procedure.[14a,b]
Imines 4b h and 5 were isolated after distillation of the crude hydro-
amination mixtures and were characterized by NMR spectroscopy, MS, IR
spectroscopy, and elemental analyses. Identification of all other products
was performed by comparison with authentic products. Compounds 4a and
4i were synthesized according to the procedures in references [16] and [9],
respectively.
Example of a typical hydroamination experiment (4b, Table 2, entry 2): A
solution of 1-octyne (3.2 mL, 2.4 g, 21.5 mmol) and tert-butylamine
(3.5 mL, 2.4 g, 32.2 mmol) was treated with
1 (0.15 g, 0.43 mmol,
2mol%) in toluene (6 mL). This mixture was heated to 85 8C and distilled
under vacuum after 24 h. Product 4b was obtained at 48 498C (0.1 mbar);
yield: 2.9 g (75%, >98% (GC) anti-Markovnikov product); 1H NMR
(400 MHz, CDCl3): d 0.85 (t, 3H, CH3), 1.14 (s, 9H, C-CH3), 1.21 1.34
(m, 8H, CH2), 1.46 (m, 2H, CH2), 2.20 (m, 2H, CH2), 7.56 ppm (t, 3J
5.35 Hz, 1H, CH); 13C NMR (100 MHz, CDCl3): d 14.0 (CH3), 22.6, 26.4,
29.1, 29.2 (CH2), 29.6 (C-CH3), 31.7, 36.4 (CH2), 56.4 (Cq), 159.3 ppm (CH);
IR (neat): nÄC N: 1671 cmÀ1; MS (EI, 70 eV): m/z 184 [M 1], 183 [M ],
168 [M À CH3], 99 [C7H15 ], 84 [C4H9NCH ], 57 [C4H9 ]; elemental
analysis C12H25N calcd (%) C 78.62, H 13.74, N 7.64; found C 78.19, H 13.99,
N 7.42.
Received: December 21, 2001 [Z18425]
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Formation of a Butadienenickel-Based
Zwitterionic Single-Component Catalyst for
Ethylene Polymerization: An Alternative
Activation Pathway for Homogeneous
Ziegler Natta Catalysts of Late Transition
Metals**
Joachim W. Strauch, Gerhard Erker,* Gerald Kehr,
and Roland Frˆhlich
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[*] Prof. Dr. G. Erker, Dipl.-Chem. J. W. Strauch, Dr. G. Kehr,
Dr. R. Frˆhlich[]
Organisch-Chemisches Institut der Universit‰t
Westf‰lische Wilhelms-Universit‰t M¸nster
Corrensstrasse 40, 48149 M¸nster (Germany)
Fax : (49)251-833-36503
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2001, 66, 6339 6343.
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2924.
[ ] X-ray crystal structure analysis.
[**] This work was supported by the Fonds der Chemischen Industrie (and
the BMBF) and the Deutsche Forschungsgemeinschaft.
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Angew. Chem. Int. Ed. 2002, 41, No. 14
¹ WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002
1433-7851/02/4114-2543 $ 20.00+.50/0
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