1084
S. Enthaler, M. Weidauer
129.8, 129.6, 115.7, 115.6, 115.2, 115.1, 1.9, –0.7 ppm; 19F
4.15 Cinnamoylnitrile (14a) [33]
NMR (CDCl3, 188 MHz) d = -108.2 (m) ppm.
1H NMR (CDCl3, 200 MHz) d = 7.35–7.48 (m, 6H), 5.78-
5.92 (m, 1H) ppm; 13C NMR (CDCl3, 50 MHz) d = 150.7,
133.5, 131.3, 129.2, 127.4, 118.2, 96.2 ppm; MS (ESI)
m/z = 129 (100, M?), 102 (44), 76 (12), 51 (18).
4.20 General Procedure for the Dehydration of Amides
A pressure tube was charged with an appropriate amount of
copper(I) chloride (0.018 mmol, 2.5 mol%), and the cor-
responding amide (0.72 mmol). After addition of toluene
(2.0 mL) 2.0 equivalents of MSTFA (1.44 mmol) were
added and the reaction mixture was stirred in a preheated
oil bath at 100 °C for 24 h. The mixture was cooled to
room temperature and an aliquot was taken for GC-analysis
(30 m Rxi-5 ms column, 40–300 °C). The reaction mixture
was dissolved in diethyl ether and purified by column
chromatography after that the solvents were removed under
reduced pressure. The analytical properties of the corre-
sponding nitriles are in agreement with literature.
4.16 Benzyl Cyanide (15a) [31]
1H NMR (CDCl3, 200 MHz) d = 7.42–7.17 (m, 5H), 3.71
(s, 2H) ppm; 13C NMR (CDCl3, 50 MHz) d = 129.4,
129.1, 128.0, 127.9, 23.6 ppm; MS (ESI) m/z = 117 (100,
M?), 90 (62), 63 (13), 51 (14).
4.17 1-Adamantylnitrile (16a) [26]
1H NMR (CDCl3, 200 MHz) d = 2.05–1.57 (m, 15H)
ppm; 13C NMR (CDCl3, 50 MHz) d = 126.2, 39.9, 35.7,
27.1, 26.3 ppm; MS (ESI) m/z = 161 (44, M?), 146 (20),
134 (100), 119 (12), 104 (16), 93 (53), 79 (25), 69 (23).
Acknowledgment Financial support from the Cluster of Excellence
‘‘Unifying Concepts in Catalysis’’ (funded by the Deutsche Fors-
¨
chungsgemeinschaft and administered by the Technische Universitat
Berlin) is gratefully acknowledged.
4.18 Synthesis of the Bissilylated Compound 24
References
The protocol has been carried out in accordance to the
work of Nagashima and co-workers [16]. 4-Fluorobenzoyl
chloride (23, 12.0 mmol) was added to a solution of lith-
ium bis(trimethylsilyl)amide (12.0 mmol) in n-hexane
(20 mL) at -78 °C. After complete addition the mixture
was slowly warmed to room temperature and stirring was
continued for 24 h. The mixture was filtered and the sol-
vent was removed to yield yellow oil, which was used
without further purifications. Yield: 87%; 1H NMR
(CDCl3, 200 MHz) d = 0.12 (s, 9H, SiMe3), 0.27 (s, 9H,
SiMe3), 6.94–7.07 (m, 2H, Ar), 7.51–7.64 (m, 2H, Ar)
ppm; 13C NMR (CDCl3, 50 MHz) d = 171.0, 168.3, 161.3,
155.1, 134.8, 134.6, 132.9, 130.6, 130.4, 129.8, 129.6,
129.0, 115.7, 115.2, 114.5, 1.9, 1.3, 0.3, -0.7 ppm; 19F
NMR (CDCl3, 188 MHz) d = -110.7 (m) ppm.
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The protocol has been carried out in accordance to litera-
ture [37]. To a solution of 1 (22.0 mmol) and triethylamine
(22.0 moml) in toluene (20 mL) was added trimethylsilyl
chloride (22.0 mmol) at room temperature under an
atmosphere of dinitrogen. The mixture was refluxed for
24 h. The solvent was removed in vacuum and the residue
was extracted with n-hexane to yield the monosilylated
1
compound 25. Yield: 63%; H NMR (CDCl3, 200 MHz)
d = 0.30 (s, 9H, SiMe3), 6.97–7.14 (m, 2H, Ar), 7.72–7.86
(m, 2H, Ar) ppm; 13C NMR (CDCl3, 50 MHz) d = 171.2,
168.4, 167.3, 162.4, 162.3, 131.3, 131.2, 130.0, 129.9,
123