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W. Zhang, M. Shi / Tetrahedron 62 (2006) 8715–8719
a Carlo-Erba 1106 analyzer. Commercially obtained re-
agents were used without further purification. All reactions
were monitored by TLC with Huanghai GF254 silica gel
coated plates. Flash column chromatography was carried
out using 300–400 mesh silica gel at increased pressure.
Reaction experiments were performed under argon condi-
tion. The starting materials 1b–1h25 were synthesized
according to the previous literature.
129.8, 130.0, 140.5, 144.9, 164.6. MS (EI) m/z: 265 (M+,
8.14), 130 (42.40), 119 (100), 91 (29.56), 65 (32.29).
4.2.6. 3,5-Dimethylbenzoic acid cyano(3,5-dimethyl-
phenyl)methyl ester (2f). A light yellow oil: 67 mg, 91%
yield. IR (CH2Cl2) n 3010, 2922, 2859, 1727, 1609, 1462,
1
1301 cmꢀ1. H NMR (CDCl3, 300 MHz, TMS): d 2.35 (s,
6H, 2CH3), 2.36 (s, 6H, 2CH3), 6.60 (s, 1H, CH), 7.10 (s,
1H, Ar), 7.21 (s, 2H, Ar), 7.24 (s, 1H, Ar), 7.67 (s, 2H,
Ar). 13C NMR (CDCl3, 75 MHz): d 21.0, 21.1, 63.2,
116.4, 125.6, 127.6, 127.9, 131.7, 131.9, 135.6, 138.2,
138.9, 164.8. MS (EI) m/z: 293 (M+, 4.18), 144 (16.48),
133 (100), 105 (11.43). HRMS (MALDI) for
C19H19NO2Na+: 316.1315; found: 316.1308.
4.2. Typical reaction procedure for the preparation of 2
A mixture of acyl cyanide (0.5 mmol) and PMe3 (0.5 mL,
0.5 mmol, 1.0 M in THF) was stirred under argon at room
temperature for the required time indicated in tables. After
the reaction solution was concentrated under reduced pres-
sure, the residue was purified by flash chromatography on
silica gel (eluent: EtOAc/petroleum¼1/20) to afford pure
product 2.
4.2.7. 3,4,5-Trimethoxybenzoic acid cyano(3,4,5-tri-
methoxyphenyl)methyl ester (2g). A yellow solid: 77 mg,
74% yield. Mp: 137–139 ꢁC. IR (CH2Cl2) n 2941, 1727,
1593, 1464, 1338, 1211 cmꢀ1. 1H NMR (CDCl3, 300 MHz,
TMS): d 3.88 (s, 3H, OCH3), 3.91 (s, 6H, 2OCH3), 3.92
(s, 6H, 2OCH3), 3.93 (s, 3H, OCH3), 6.63 (s, 1H, CH), 6.82
(s, 2H, Ar), 7.31 (s, 2H, Ar). 13C NMR (CDCl3, 75 MHz):
d 56.1, 56.2, 60.7, 60.8, 63.5, 105.0, 107.2, 116.1, 122.7,
127.0, 139.4, 143.1, 152.9, 153.6, 164.2. MS (EI) m/z: 418
(M++1, 18.88), 205 (100), 194 (88.24), 93 (1.41), 81 (4.68).
Anal. Calcd for C21H23NO8: C, 60.43%; H, 5.55%; N,
3.36%; found: C, 60.40%; H, 5.64%; N, 3.13%.
4.2.1. Benzoic acid cyano-phenyl-methyl ester (2a)
(a known compound).26 An off-white solid: 47 mg, 80%
yield. H NMR (CDCl3, 300 MHz, TMS): d 6.68 (s, 1H,
1
CH), 7.45–7.50 (m, 6H, Ar), 7.60–7.65 (m, 2H, Ar), 8.06–
8.09 (m, 2H, Ar). 13C NMR (CDCl3, 75 MHz): d 63.3,
116.2, 127.8, 128.0, 128.6, 129.2, 130.0, 130.4, 131.8,
134.1, 164.6. MS (EI) m/z: 237 (M+, 3.73), 116 (28.30),
105 (100), 77 (25.62).
4.2.2. 4-Chlorobenzoic acid (4-chlorophenyl)-cyano-
methyl ester (2b) (a known compound).15 A light yellow
solid: 68 mg, 89% yield. 1H NMR (CDCl3, 300 MHz,
TMS): d 6.63 (s, 1H, CH), 7.44–7.48 (m, 4H, Ar), 7.55 (d,
J¼8.1 Hz, 2H, Ar), 7.98 (d, J¼8.4 Hz, 2H, Ar). 13C NMR
(CDCl3, 75 MHz): d 62.8, 115.6, 126.2, 129.0, 129.3,
129.5, 130.1, 131.3, 136.7, 140.8, 163.6.
4.2.8. Cyano(furan-2-yl)methyl furan-2-carboxylate
(2h). A yellow solid: 40 mg, 74% yield. Mp: 122–124 ꢁC.
IR (CH2Cl2) n 2923, 1732, 1470, 1394, 1280, 1099 cmꢀ1
.
1H NMR (CDCl3, 300 MHz, TMS): d 6.46–6.48 (m, 1H,
Fu), 6.55–6.57 (m, 1H, Fu), 6.72 (s, 1H, CH), 6.76–6.78
(m, 1H, Fu), 7.32–7.33 (m, 1H, Fu), 7.53–7.55 (m, 1H,
Fu), 7.64–7.66 (m, 1H, Fu). 13C NMR (CDCl3, 75 MHz):
d 55.8, 111.1, 112.3, 113.0, 116.9, 120.5, 142.3, 145.2,
146.3, 147.8, 156.1. MS (EI) m/z: 217 (M+, 1.74), 106
(89.00), 95 (100), 77 (15.07), 51 (19.96). HRMS (EI) for
C11H7NO4: 217.0375; found: 217.0380.
4.2.3. 3-Chlorobenzoic acid (3-chlorophenyl)-cyano-
methyl ester (2c). A light yellow oil: 60 mg, 78% yield.
IR (CH2Cl2) n 1738, 1428, 1243, 1196, 1120, 1069 cmꢀ1
.
1H NMR (CDCl3, 300 MHz, TMS): d 6.63 (s, 1H, CH),
7.41–7.51 (m, 4H, Ar), 7.59–7.63 (m, 2H, Ar), 7.94–7.98
(m, 1H, Ar), 8.02–8.04 (m, 1H, Ar). 13C NMR (CDCl3,
75 MHz): d 62.9, 115.4, 126.0, 128.0, 128.2, 129.4, 130.0,
130.1, 130.7, 130.8, 133.2, 134.3, 134.9, 135.3, 163.3. MS
(EI) m/z: 306 (M+, 2.26), 150 (22.58), 139 (100), 111
(22.35), 75 (23.83). HRMS (EI) for C15H9NO2Cl2:
305.0010; found: 305.0016.
Acknowledgements
We thank the State Key Project of Basic Research (Project
973) (No. G2000048007), Shanghai Municipal Committee
of Science and Technology (04JC14083), and the National
Natural Science Foundation of China (20472096,
203900502, and 20272069) for financial support.
4.2.4. 2-Chlorobenzoic acid (2-chlorophenyl)-cyano-
methyl ester (2d) (a known compound).15 A white solid:
40 mg, 52% yield. 1H NMR (CDCl3, 300 MHz, TMS):
d 6.96 (s, 1H, CH), 7.33–7.51 (m, 6H, Ar), 7.81–7.84 (m,
1H, Ar), 7.91 (d, J¼7.5 Hz, 1H, Ar). 13C NMR (CDCl3,
75 MHz): d 61.1, 115.1, 126.8, 127.4, 127.7, 129.2, 129.7,
130.3, 131.5, 131.8, 132.0, 133.6, 133.8, 134.7, 163.1.
References and notes
1. For general applications, see: (a) Veum, L.; Kanerva, L. T.;
Halling, P. J.; Maschmeyer, T.; Hanefeld, U. Adv. Synth.
Catal. 2005, 347, 1015–1021; (b) North, M. Tetrahedron
2004, 60, 10371–10568; (c) Vachal, P.; Jacobsen, E. N.
Comprehensive Asymmetric Catalysis; Jacobsen, E. N.,
Pfaltz, A., Yamamoto, H., Eds.; Supplement 1, pp 117–129;
(d) Gregory, R. J. H. Chem. Rev. 1999, 99, 3649–3682; (e)
Effenberger, F. Angew. Chem., Int. Ed. Engl. 1994, 106,
1609–1619; (f) North, M. Synlett 1993, 807–820.
4.2.5. 4-Methylbenzoic acid cyano(4-methylphenyl)-
methyl ester (2e) (a known compound).15 A white solid:
52 mg, 78% yield. 1H NMR (CDCl3, 300 MHz, TMS):
d 2.40 (s, 3H, CH3), 2.42 (s, 3H, CH3), 6.62 (s, 1H, CH),
7.26 (t, J¼6.6 Hz, 4H, Ar), 7.50 (d, J¼8.1 Hz, 2H, Ar),
7.94 (d, J¼8.1 Hz, 2H, Ar). 13C NMR (CDCl3, 75 MHz):
d 21.2, 21.7, 63.0, 116.4, 125.3, 127.8, 129.0, 129.3,
2. (a) Brunel, J.-M.; Holmes, I. P. Angew. Chem., Int. Ed. 2004,
116, 2810–2837; (b) North, M. Tetrahedron: Asymmetry