(2), 52 (5); m/z (ESI) 263.1752 ([M + NH4]+, C15H23N2O2 requires
(Ar-CH), 109.8 (Ar-CH), 117.4 (CN), 122.8 (Ar-CH), 130.2
263.1754).
(i-Ar-C), 147.4 (Ar-C(OCH2)), 148.3 (Ar-C(OCH2)), 205.4
+
=
(C O); m/z (CI + NH3) 277 ([M + NH4] , 100%), 252 (5), 52
(15); m/z (ESI) 277.1546 ([M + NH4]+, C15H21N2O3 requires
4,4-Dimethyl-3-oxo-2-(4-methoxybenzyl)pentanenitrile,
29d.
Prepared from p-methoxybenzyl alcohol 1d (414 mg, 3 mmol)
with 4,4-dimethyl-3-oxopentanenitrile 28 (376 mg, 3 mmol). The
crude mixture was purified by flash column chromatography,
277.1547).
Acknowledgements
◦
eluting with 9 : 1 petroleum ether (bp 40–60 C)–EtOAc to give
the title compound 29d as a colourless oil (350 mg, 48% isolated
yield) (Found: C, 73.43; H, 7.90; N, 5.75. C15H19NO2 requires
C, 73.44; H, 7.81; N, 5.71%); mmax(film)/cm−1 2967 (C–C), 2255
We would like to thank the EPSRC and the British Council for
support of this work.
=
(C≡N), 1722 (C O), 1613, 1514, 1251, 1179, 1035; dH (300 MHz;
References
CDCl3; Me4Si) 1.01 (9H, s, 3 × CH3), 2.98 (1H, dd, JHH 13.7
and 7.6, CHAHB), 3.07 (1H, dd, JHH 13.7 and 7.6, CHAHB), 3.69
(3H, s, OCH3), 3.92 (1H, dd, JHH 7.6 and 7.6, CH(CN)CH2Ph),
6.75 (2H, d, JHH 8.7, m-Ph-H), 7.04 (2H, d, JHH 8.7, o-Ph-H); dC
(75.5 MHz; CDCl3; CDCl3) 24.6 (3 × CH3), 34.2 (CHCH2Ph),
38.0 (CHCH2Ph), 44.5 ((CH3)3CC(O)), 54.2 (OCH3), 113.2
1 For reviews see: (a) G. Zassinovich and G. Mestroni, Chem. Rev., 1992,
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(m-Ph-C), 116.2 (CN), 127.2 (i-Ph-C), 129.2 (o-Ph-C), 158.0
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=
(p-Ph-C), 204.1 (C O); m/z (CI + NH3) 263 ([M + NH4] ,
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4,4-Dimethyl-3-oxo-2-(4-fluorobenzyl)pentanenitrile, 29g. Pre-
pared from p-fluorobenzyl alcohol 1g (327 lL, 3 mmol) with 4,4-
dimethyl-3-oxopentanenitrile 28 (376 mg, 3 mmol). The crude
mixture was purified by flash column chromatography, eluting
with 9 : 1 petroleum ether (bp 40–60 ◦C)–EtOAc to give the
title compound 29g as a yellow oil (212 mg, 30.4% isolated yield)
(Found: C, 72.03; H, 6.88; N, 6.04. C14H16FNO requires C, 72.08;
H, 6.91; N, 6.00%); mmax(film)/cm−1 2963 (C–C), 2254 (C≡N), 1723
=
(C O), 1511, 1226; dH (300 MHz; CDCl3; Me4Si) 1.02 (9H, s,
3 × CH3), 3.02 (1H, dd, JHH 13.7 and 7.6, CHAHB), 3.10 (1H,
dd, JHH 13.7 and 7.6, CHAHB), 3.94 (1H, dd, JHH 7.6 and 7.6,
CH(CN)CH2Ph), 6.92 (2H, m, m-Ph-H), 7.11 (2H, m, o-Ph-H);
dC (75.5 MHz; CDCl3; CDCl3) 24.8 (3 × CH3), 34.0 (CHCH2Ph),
37.8 (CHCH2Ph), 44.5 ((CH3)3CC(O)), 114.4 (2C, d, JCF 21.5, m-
Ph-C), 115.9 (CN), 129.8 (2C, d, JCF 8.1, o-Ph-C), 131.0 (1C, d,
=
JCF 3.3, i-Ph-C), 161.2 (1C, d, JCF 246.3, p-Ph-C), 203.8 (C O);
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dF(376.5 MHz; CDCl3) −114.6 (1F, s, Ph-F); m/z (CI + NH3) 251
([M + NH4]+, 100%), 233 (5), 226 (33), 208 (3), 186 (6), 171 (2); m/z
(ESI) 251.1553 ([M + NH4]+, C14H20N2OF requires 251.1554).
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4,4-Dimethyl-3-oxo-2-(3,4-methylenedioxybenzyl)pentanenitrile,
29i. Prepared from 3,4-(methylenedioxy)benzyl alcohol 1i
(456 mg, 3 mmol) with 4,4-dimethyl-3-oxopentanenitrile 28
(376 mg, 3 mmol). The crude mixture was purified by flash
column chromatography, eluting with 9 : 1 petroleum ether (bp
40–60 C)–EtOAc to give the title compound 29i as a colourless
oil (358 mg, 46% isolated yield) (Found: C, 69.40; H, 6.65; N, 5.45.
C15H17NO3 requires C, 69.48; H, 6.61; N, 5.40%); mmax(film)/cm−1
◦
=
2970, 2928, 2891, 2260 (C≡N), 1719 (C O), 1507, 1501, 1448,
1369, 1247, 1040; dH (300 MHz; CDCl3; Me4Si) 1.12 (9H, s,
3 × CH3), 3.03 (1H, dd, JHH 13.7 and 7.6, CHAHB), 3.11 (1H,
dd, JHH 13.7 and 7.6, CHAHB), 3.99 (1H, dd, JHH 7.6 and 7.6,
CH(CN)CH2Ph), 5. 3 (2H, s, OCH2O), 6.63–6.75 (3H, m, Ph-H);
dC (75.5 MHz; CDCl3; CDCl3) 26.0 (3 × CH3), 36.1 (CHCH2Ar),
39.4 (CHCH2Ar), 45.9 ((CH3)3CC(O)), 101.5 (OCH2O), 108.9
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