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2-(Benzoyloxy)-4-phenylbutanenitrile (3o)
Colourless oil.; Rf 0.40 (n-hexane–EtOAc, 4:1).
IR (neat): 2333, 1731, 1263 cm–1.
13C NMR (75 MHz, CDCl3): d = 20.4 (CH3), 61.5 (CCN), 118.2
(CN), 127.1, 128.8, 129.1, 129.4, 134.3, 137.8 (C=C, ArC), 168.9
(C=O).
1H NMR (300 MHz, CDCl3): d = 2.35–2.43 (m, 2 H, CH2CHO),
2.93 (t, J = 7.6 Hz, 2 H, CH2Ph), 5.53 (d, J = 6.7 Hz, 1 H, CHO),
7.19–7.25 (m, 3 H, ArH), 7.31–7.34 (m, 2 H, ArH), 7.47 (t, J = 7.5,
2 H, ArH), 7.60–7.65 (m, 1 H, ArH), 8.01 (d, J = 7.2, 2 H, ArH).
13C NMR (75 MHz, CDCl3): d = 30.8 (CH2CHO), 33.9 (CH2Ar),
61.0 (CH), 116.7 (CN), 126.7, 128.1, 128.3, 128.6, 129.8, 130.0,
134.0, 139.0 (ArC), 164.7 (CO).
Acknowledgment
This work was supported by the DGES of the Spanish Ministerio de
Educación y Cultura (MEC) (BQU2001-0724, CTQ2004-02375/
BQU and CTQ 2004-00808/BQU) and Generalitat Valenciana
(CTIOIB/2002/320 and GRUPOS03/134) and by the University of
Alicante. A. Baeza thanks Generalitat Valenciana for a pre-doctoral
fellowship (CTBPRB/2002/107).
MS (EI): m/z = 266 (M+ + 1, 0.05), 143 (100), 116 (20), 105 (32).
HRMS: m/z calcd for C17H16NO2 (M+ + 1): 266.2181; found:
266.2183.
References
(1) Tanaka, K. Solvent-Free Organic Synthesis; Wiley-VCH:
Weinheim, 2003.
1-(Benzoyloxy)-4-tert-butylcyclohexanecarbonitrile (3u)
White prisms; mp 109 °C (n-hexane–EtOAc); Rf 0.55 (n-hexane–
EtOAc, 4:1).
IR (KBr): 2366, 1729, 1278 cm–1.
1H NMR (300 MHz, CDCl3): d = 0.91 (s, 9 H, 3 CH3), 1.06–1.17
(m, 1 H, CH), 1.46–1.60 (m, 2 H, CH2), 1.69–1.79 (m, 2 H, CH2),
1.91–1.96 (m, 2 H, CH2), 2.70–2.74 (m, 2 H, CH2), 7.46 (t, J = 7.6
Hz, 2 H, ArH), 7.60 (m, 1 H, ArH), 8.03 (m, 2 H, ArH).
(2) (a) Chen, F.-X.; Feng, X. Synlett 2005, 892. (b) Synthesis
and Applications of Non-Racemic Cyanohydrins and a-
Amino Acids, Tetrahedron Symposium in Print, Vol. 60;
North, M., Ed.; Elsevier: London, 2004, 10371–10568.
(c) Brunel, J.-M.; Holmes, I. P. Angew. Chem. Int. Ed. 2004,
43, 2752. (d) North, M. Tetrahedron: Asymmetry 2003, 14,
147.
13C NMR (75 MHz, CDCl3): d = 23.9 (CH2), 27.5 [C(CH3)3], 32.3
[C(CH3)3], 35.6 (CH2C), 46.8 (CH), 74.2 (CCN), 118.1 (CN),
128.5, 129.2, 129.8, 133.6 (ArC), 164.4 (C=O).
MS (EI): m/z = 285 (M+ + 1, 0.2), 163 (22), 124 (16), 106 (26), 105
(100).
(3) Au, A. T. Synth. Commun. 1984, 14, 743.
(4) Thanasa, N.; Prachyawarakorn, V.; Tontoolarug, S.;
Ruchirawat, S. Tetrahedron Lett. 2003, 44, 1019.
(5) Shin, D.-S.; Jung, Y.-S.; Kim, J.-J.; Ahn, C. Bull. Korean
Chem. Soc. 1998, 19, 119.
(6) Scholl, M.; Lim, C.-K.; Fu, G. C. J. Org. Chem. 1995, 60,
6229.
Anal. Calcd for C18H23NO3: C, 75.7; H, 8.1; N, 4.9. Found: C, 75.8;
H, 8.2; N, 4.9.
(7) Deardorff, D. R.; Taniguchi, C. M.; Tafti, S. A.; Kim, H. Y.;
Choi, S. Y.; Downey, K. J.; Nguyen, T. V. J. Org. Chem.
2001, 66, 7191.
2-(Acetoxy)-2-phenylacetonitrile (4a)14e,19b
(8) Berthiaume, D.; Poirier, D. Tetrahedron 2000, 56, 5995.
(9) Linghu, X.; Nicewicz, D. A.; Johnson, J. S. Org. Lett. 2002,
4, 2957.
(10) Okimoto, M.; Chiba, T. Synthesis 1996, 1188.
(11) Hoffmann, H. M. R.; Ismail, Z. M.; Hollweg, R.; Zein, A. R.
Bull. Chem. Soc. Jpn. 1990, 63, 1807.
Colourless sticky oil.
1H NMR (300 MHz, CDCl3): d = 2.16 (s, 3 H, CH3), 6.40 (s, 1 H,
CHCN), 7.44–7.47 (m, 3 H, ArH), 7.50–7.53 (m, 2 H, ArH).
13C NMR (75 MHz, CDCl3): d = 20.4 (CH3), 62.8 (CHCN), 116.1
(CN), 127.8, 129.2, 130.4, 131.7 (ArC), 168.9 (C=O).
(12) Micó, I.; Nájera, C. Tetrahedron 1993, 49, 4327.
(13) Baeza, A.; Nájera, C.; Sansano, J. M. Arkivoc 2005, ix, 353;
2-(Acetoxy)-2-(3-phenoxyphenyl)acetonitrile (4g)15d
Colourless oil.
1H NMR (300 MHz, CDCl3): d = 2.17 (s, 3 H, CH3), 6.35 (s, 1 H,
CHCN), 7.01–7.07 (m, 3 H, ArH), 7.14–7.26 (m, 3 H, ArH), 7.35–
7.42 (m, 3 H, ArH).
13C NMR (75 MHz, CDCl3): d = 20.4 (CH3), 62.3 (CHCN), 117.6
(CN), 119.3, 119.4, 120.0, 122.0, 124.1, 129.9, 130.0, 130.6, 133.4,
156.1, 168.8 (C=O).
(14) For the synthesis of non-racemic O-alkoxycarbonyl
cyanohydrins: (a) Tian, S.-K.; Deng, L. J. Am. Chem. Soc.
2001, 123, 6195. (b) Tian, J.; Yamagiwa, N.; Matsunaga, S.;
Shibasaki, M. Angew. Chem. Int. Ed. 2002, 41, 3636.
(c) Casas, J.; Baeza, A.; Sansano, J. M.; Nájera, C.; Saá, J.
M. Tetrahedron: Asymmetry 2003, 14, 197. (d) Belokon’,
Y. N.; Blacker, A. J.; Clutterbuck, L. A.; North, M. Org.
Lett. 2003, 5, 4505. (e) Belokon’, Y. N.; Blacker, A. J.;
Carta, P.; Clutterbuck, L. A.; North, M. Tetrahedron 2004,
60, 10433. (f) Yamagiwa, N.; Tian, J.; Matsunaga, S.;
Shibasaki, M. J. Am. Chem. Soc. 2005, 127, 3413.
(15) For the synthesis of non-racemic O-acyl or O-benzoyl
cyanohydrins, see: (a) Baeza, A.; Nájera, C.; Sansano, J. M.
Tetrahedron: Asymmetry, in press. (b)Huang, W.; Song, Y.;
Bai, C.; Cao, G.; Zheng, Z. Tetrahedron Lett. 2004, 45,
4763. (c) Belokon’, Y. N.; Carta, P.; North, M. Lett. Org.
Chem. 2004, 1, 81. (d) Belokon’, Y. N.; Carta, P.; Gutnov,
A. V.; Maleev, V.; Moskalenko, M. A.; Yashkina, L. V.;
Ikonnikov, N. S.; Voskoboev, N. V.; Khrustalev, V. N.;
North, M. Helv. Chim. Acta 2002, 85, 3301. (e) Belokon’,
Y. N.; Gutnov, A. V.; Moskalenko, M. A.; Yashkina, L. V.;
Lesovoy, D. E.; Ikonnikov, N. S.; Larichev, V. S.; North, M.
Chem. Commun. 2002, 244.
(E)-2-(Acetoxy)non-3-enenitrile (4l)43
Colourless oil.
1H NMR (300 MHz, CDCl3): d = 0.89 (t, J = 6.7 Hz, 3 H, CH3CH2),
1.26–1.32 (m, 4 H, 2 CH2), 1.38–1.43 (m, 2 H, CH2), 2.09–2.16 (m,
2 H, CH2CH), 2.14 (s, 3 H, CH3CO), 5.51–5.59 (m, 1 H, CHCH-
CN), 5.79 (d, J = 6.6 Hz, 1 H, CHCN), 6.10–6.20 (m, 1 H, CH2CH).
13C RMN (75 MHz, CDCl3): d = 13.8 (CH3CH2), 20.3 (CH3CO),
22.3 (CH2), 27.8 (CH2), 31.1 (CH2), 31.9 (CH2), 61.4 (CHCN),
115.7 (CN), 119.8 (CHCHCN), 140.7 (CH2CH), 168.9 (C=O).
(E)-2-(Acetoxy)-4-phenylbut-3-enenitrile (4m)44
Colourless oil.
1H NMR (300 MHz, CDCl3): d = 2.18 (s, 3 H, CH3), 6.03 (d, J = 6.7
Hz, 1 H, CHCN), 6.20 (dd, J = 6.7, 15.7 Hz, 1 H, CH=CHCH), 6.97
(d, J = 15.7 Hz, 1 H, PhCH), 7.35–7.45 (m, 5 H, ArH).
Synthesis 2005, No. 16, 2787–2797 © Thieme Stuttgart · New York