R. Chinchilla et al. / Tetrahedron: Asymmetry 20 (2009) 2279–2286
2285
k = 210 nm, n-hexane/2-propanol, 99/1, 1.0 mL/min, tr (ma-
jor) = 22.0 min, tr (minor) = 30.7 min.
4.3.14. (R)-Anthracen-9-yl(cyano)methyl methyl carbonate 6as
Yellow solid, mp 153–155 °C; IR (KBr)
1755, 1274 cmÀ1 1H
m
;
NMR: dH 3.83 (3H, s, OCOOCH3), 7.50–7.54 (2H, m, ArH), 7.64–
7.69 (2H, m, ArH), 7.85 (1H, s, CHCN), 8.04 (2H, d, J = 8.2 Hz,
ArH), 8.48 (2H, d, J = 9.0 Hz, ArH), 8.59 (1H, s, ArH); 13C NMR: dC
56.1, 60.8, 116.5, 120.9, 123.2, 125.6, 128.1, 129.6, 130.2, 131.4,
132.1, 154.6; MS (EI): m/z (%) 291 (M+, 24), 216 (100); HRMS calcd
for C18H13NO3: 291.0895, found 291.0933; HPLC: Chiracel OD-H,
k = 254 nm, n-hexane/2-propanol, 90:10, 1.0 mL/min, tr (min-
or) = 17.5 min, tr (major) = 29.2 min.
4.3.8. (R)-4-Cyano(methoxycarbonyloxy)methyl)phenyl acetate
6ak
Colorless oil; IR (film):
m
1759, 1259, 1201; 1H NMR: dH 2.32
(3H, s, OCOCH3), 3.87 (3H, s, OCOOCH3), 6.27 (1H, s, CHCN), 7.20
(2H, d, J = 8.6 Hz, ArH), 7.57 (2H, d, J = 8.7 Hz, ArH); 13C NMR: dC
21.2, 56.1, 66.0, 115.6, 122.7, 128.7, 129.4, 152.4, 154.1, 169.1;
MS (EI): m/z (%) 249 (M+, 8), 131 (100); HRMS calcd for
C12H11NO5: 249.0637, found 249.0572; HPLC: Chiracel AD,
k = 210 nm, n-hexane/2-propanol, 97:3, 1.0 mL/min, tr (min-
or) = 28.9 min, tr (major) = 31.2 min.
4.3.15. (R)-Cyano(1-(phenylsulfonyl)-1H-pyrrol-2-yl)methyl
methyl carbonate 6at
Colorless oil; IR (film): m
1762, 1265 cmÀ1; 1H NMR: dH 3.88 (3H,
s, OCOOCH3), 6.34–6.36 (1H, m, ArH), 6.72 (1H, s, CHCN), 6.83–6.84
(1H, m, ArH), 7.38–7.40 (1H, m, ArH), 7.51–7.56 (2H, m, ArH), 7.63–
7.68 (1H, m, ArH), 7.81–7.84 (2H, m, ArH); 13C NMR: dC 55.9, 59.1,
112.3, 114.6, 119.6, 123.5, 126.2, 126.8, 129.6, 134.5, 138.3, 153.6;
MS (EI): m/z (%) 245 (M+-75, 11), 77 (100); HPLC: Chiracel AD,
k = 210 nm, n-hexane/2-propanol, 90:10, 1.0 mL/min, tr (min-
or) = 18.0 min, tr (major) = 22.3 min.
4.3.9. (R)-(4-(tert-Butyldimethylsilyloxy)phenyl)(cyano)methyl
methyl carbonate 6al
Colorless oil; IR (film):
m
1759, 1254; 1H NMR: dH 0.21 (6H, s,
2 Â SiCH3), 0.98 (9H, s, SiC(CH3)3), 3.86 (3H, s, OCOOCH3), 6.20
(1H, s, CHCN), 6.89 (2H, d, J = 8.6 Hz, ArH), 7.41 (2H, d, J = 8.4 Hz,
ArH); 13C NMR: dC À4.3, 18.3, 25.7, 55.9, 66.5, 116.0, 120.9,
123.9, 129.8, 154.3, 158.0; MS (EI): m/z (%) 321 (M+, 9), 89 (100);
HRMS calcd for C16H23NO4Si: 321.1396, found 321.1429; HPLC:
Chiracel OG, k = 210 nm, n-hexane/2-propanol, 95:5, 1.0 mL/min,
tr (major) = 5.6 min, tr (minor) = 6.6 min.
4.3.16. (R)-(1-Acetyl-1H-indol-3-yl)(cyano)methyl methyl
carbonate 6au
Colorless oil; IR (film):
m
2215, 1759, 1465, 1388, 1260 cmÀ1; 1H
4.3.10. (R)-Cyano(4-(methylthio)phenyl)methyl methyl
NMR: dH 2.66 (3H, s, NCOCH3), 3.88 (3H, s, OCOOCH3), 6.54 (1H, s,
CHCN), 7.36 (1H, t, J = 7.7 Hz, ArH), 7.43 (1H, t, J = 8.2 Hz, ArH), 7.68
(1H, d, J = 7.7 Hz, ArH), 7.73 (1H, s, ArH), 8.44 (1H, d, J = 8.4 Hz,
ArH); 13C NMR: dC 24.0, 56.1, 59.9, 113.1, 115.1, 117.0, 119.0,
124.6, 126.3, 126.6, 126.8, 136.1, 154.2, 168.5; MS (EI): m/z (%) 272
(M+, 14), 154 (100); HRMS calcd for C14H12N2O4: 272.0797, found
272.0806; HPLC: Chiracel AD, k = 210 nm, n-hexane/2-propanol,
95:5, 0.9 mL/min, tr (minor) = 33.3 min, tr (major) = 36.5 min.
carbonate 6am
Colorless oil; IR (film): m
1758, 1255 cmÀ1; 1H NMR: dH 2.49 (3H,
s, PhSCH3), 3.86 (3H, s, OCOOCH3), 6.22 (1H, s, CHCN), 7.28 (2H, d,
J = 8.4 Hz, ArH), 7.44 (2H, d, J = 8.4 Hz, ArH); 13C NMR: dC 15.3, 56.0,
66.4, 115.7, 126.4, 127.5, 128.5, 142.7, 154.2; MS (EI): m/z (%) 237
(M+, 30), 162 (100); HRMS calcd for C11H11NO3S: 237.0460, found
237.0483; HPLC: Chiracel OD-H, k = 210 nm, n-hexane/2-propanol,
90:10, 1.0 mL/min, tr (major) = 9.9 min, tr (minor) = 11.9 min.
4.3.17. (S)-Cyano(furan-2-yl)methyl methyl carbonate 6av
4.3.11. (R)-(4-Chlorophenyl)(cyano)methyl methyl carbonate
Colorless oil; IR (film): m
2254, 1763 cmÀ1; 1H NMR: dH 3.89 (3H,
6ao
Colorlessoil; IR (film): m
2247, 1767 cmÀ1; 1H NMR: dH 3.90 (3H, s,
s, OCOOCH3), 6.36 (1H, s, CHCN), 6.46 (1H, dd, J = 3.3, 1.9 Hz,
OCHCH), 6.75 (1H, d, J = 3.3 Hz, OCCH), 7.53 (1H, d, J = 1.9 Hz,
OCHCH); 13C NMR: dC 55.9, 59.3, 111.1, 113.0, 113.6, 143.4,
145.2, 153.8; MS (EI) m/z (%) 181 (M+, 18), 106 (100); HRMS calcd
for C8H7NO4: 181.0375, found 181.0376; HPLC: Chiralpak AD,
k = 210 nm, n-hexane/2-propanol, 99/1, 1.0 mL/min, tr (ma-
jor) = 13.0 min, tr (minor) = 14.7 min.
OCOOCH3), 6.26 (1H, s, CHCN), 7.44–7.53 (4H, m, ArH); 13C NMR: dC
55.9, 65.7, 115.2, 128.1, 129.2, 129.5, 130.8, 153.8; MS (EI): m/z (%)
225 (M+, 32), 150 (100); HRMS calcd for C10H8ClNO3: 225.0192,
found 225.0188; HPLC: Chiracel OG, k = 210 nm, n-hexane/2-propa-
nol, 99/1, 1.0 mL/min, tr (major) = 15.3 min, tr (minor) = 18.8 min.
4.3.12. (R)-Cyano(naphthalen-1-yl)methyl methyl carbonate
6aq
4.3.18. (S)-Cyano(thiophen-2-yl)methyl methyl carbonate 6aw
Colorless oil; IR (film): m
2223, 1756 cmÀ1; 1H NMR: dH 3.74 (3H,
Colorless oil; IR (film): m
1759, 1261 cmÀ1; 1H NMR: dH 3.88 (3H,
s, OCOOCH3), 6.53 (1H, s, CHCN), 7.07–7.13 (1H, m, ArH), 7.41–7.45
(1H, m, ArH), 7.54–7.64 (2H, m, ArH), 7.73–7.78 (1H, m, ArH), 8.05–
8.09 (1H, m, ArH), 8.15–8.21 (1H, m, ArH); 13C NMR: dC 55.1, 73.0,
114.9, 125.1, 125.8, 126.3, 126.4, 127.5, 128.9, 134.2, 140.4, 153.3;
MS (EI): m/z (%) 241 (M+, 20), 165 (100); Chiracel OG, k = 210 nm,
n-hexane/2-propanol, 99/1, 1.0 mL/min, tr (major) = 16.2 min, tr
(minor) = 19.4 min.
s, OCOOCH3), 6.50 (1H, s, CHCN), 7.06 (1H, dd, J = 5.2, 3.7 Hz,
SCHCH), 7.39 (1H, d, J = 3.6 Hz, SCCH), 7.49 (1H, d, J = 5.2 Hz,
SCHCH); 13C NMR: dC 56.1, 61.8, 115.1, 127.4, 129.6, 130.2, 132.7,
154.0; MS (EI): m/z (%) 197 (M+, 23), 122 (100); HRMS calcd for
C8H7NO3S: 197.0147, found 197.0175; HPLC: Chiralpak AD,
k = 254 nm, n-hexane/2-propanol, 99:1, 1.0 mL/min, tr (ma-
jor) = 13.6 min, tr (minor) = 14.9 min.
4.3.13. (R)-Cyano(naphthalen-2-yl)methyl methyl carbonate
4.3.19. (R,E)-1-Cyanobut-2-enyl methyl carbonate 7aa
6ar
Colorless oil; IR (film): m
2254, 1759 cmÀ1; 1H NMR: dH 1.83 (3H,
Colorless oil; IR (film)
m
2249, 1770 cmÀ1; 1H NMR: dH 3.89 (3H,
d, J = 6.6 Hz, CH3CH), 3.87 (3H, s, OCOOCH3), 5.58–5.68 (2H, m,
CHCN, CNCHCH), 6.22 (1H, m, CHCH=CH); 13C NMR: dC 17.6, 55.6,
65.0, 115.2, 120.8, 136.4, 153.9; MS (EI): m/z (%) 155 (M+, 7), 53
(100); HRMS calcd for C7H9NO3: 155.0582, found 155.0582; GLC:
Cyclosil-B, Tinjector = 250 °C, Tdetector = 260 °C, Tcolumn = 105 °C
(1 min) to 180 °C (2.0 °C/min), P = 120 kPa, tr (major) = 5.1 min, tr
(minor) = 5.8 min.
s, OCOOCH3), 6.44 (1H, s, CHCN), 7.57 (3H, m, ArH), 7.90 (3H, m,
ArH), 8.04 (1H, s, ArH); 13C NMR: dC 55.8, 66.7, 115.6, 124.0,
127.0, 127.6, 127.7, 128.0, 128.2, 128.3, 129.4, 132.7, 133.9,
154.0; MS (EI): m/z 241 [M]+; HRMS calcd for C14H11NO3:
241.0739, found 241.0732; HPLC: Chiracel OG, k = 210 nm, n-hex-
ane/2-propanol, 99/1, 1.0 mL/min, tr (major) = 17.3 min, tr
(minor) = 21.8 min.