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G. Guanti, R. Ri6a / Tetrahedron: Asymmetry 12 (2001) 1185–1200
1630, 1372, 1228, 1085, 1019, 960. GC–MS: Rt 6.98;
m/z 229 (M+, 0.56); 187 (5.2); 186 (35); 170 (29); 169
(49); 168 (30); 167 (7.6); 159 (14); 158 (100); 143 (11);
130 (6.4); 129 (13); 128 (27); 115 (5.4); 102 (8.6); 101
0.99 [3H, t, -CH2CH2CH3, J=7.4]; 1.58 [2H, sextuplet,
-CH2CH2CH3, J=7.2]; 2.16 [3H, s, -COCH3]; 2.29 [2H,
dt, -CH2CH2CH3, J=6.8, 2.2]; 6.67 [1H, t, CHOAc,
J=2.1]; 7.63 [1H, ddd, H7, J=8.0, 7.0, 1.2]; 7.73 [1H,
dt, H6, J=7.0, 1.4]; 7.87 [1H, d, H5, J=8.0]; 7.93 [1H,
s, H4]; 8.00 [1H, d, H8, J=7.6]; 9.28 [1H, s, H1]. 13C
NMR: 13.42 [-CH2CH2CH3]; 20.82 [-CꢀCCH2-]; 21.06
[-COCH3]; 21.75 [-CH2CH2CH3]; 66.98 [CHOAc];
76.28 [CH-CꢀCH]; 88.56 [CH-CꢀCH]; 118.51 [C4];
126.85, 127.46 and 127.68 [3C, C5, C7, C8]; 128.16 [C8a];
130.63 [C6]; 136.00 [C4a]; 149.59 [C3]; 152.70 [C1]; 169.74
[CO].
1
(6.5); 77 (12); 51 (5.8); 43 (47). H NMR: 0.93 [3H, t,
-CH2CH3, J=7.4]; 2.09 [2H, centre of m, -CH2CH3];
2.16 [3H, s, -COCH3]; 5.91 [1H, t, CHOAc, J=6.7];
7.59 [1H, ddd, H7, J=8.0, 6.8, 1.3]; 7.65 [1H, s, H4];
7.70 [1H, ddd, H6, J=8.1, 6.8, 1.4]; 7.82 [1H, d, H5,
J=8.1]; 7.97 [1H, d, H8, J=7.4]; 9.25 [1H, s, H1]. 13C
NMR: 9.71 [-CH2CH3]; 21.20 [-COCH3]; 27.65
[-CH2CH3]; 77.80 [CHOAc]; 117.78 [C4]; 126.63, 127.29
and 127.46 [3C, C5, C6, C7]; 127.97 [C8]; 127.83 [C8a];
130.49 [C6]; 136.00 [C4a]; 152.32 [C3]; 152.42 [C1]; 170.51
[CO].
4.12.6. ( )-Acetic acid 1-(isoquinolin-3-yl)prop-2-ynyl
ester 10f. Yield after chromatography: 97% (colourless
oil). Rf 0.49 (PE–Et2O 3:7, A). IR: wmax 3302, 3008,
2130, 1738, 1630, 1370, 1203, 1015, 946. GC–MS: Rt
7.14; m/z 225 (M+, 2.4); 183 (35); 182 (100); 166 (11);
164 (8.1); 156 (8.4); 154 (8.0); 140 (7.1); 139 (14); 138
(5.7); 130 (5.0); 129 (16); 128 (46); 101 (5.8); 77 (6.4); 63
(8.0); 51 (5.8); 43 (6.4). 1H NMR: 2.19 [3H, s,
-COCH3]; 2.73 [1H, d, -CꢀCH, J=2.2]; 6.68 [1H, d,
CHOAc, J=2.2]; 7.65 [1H, dt, H7, J=8.0, 1.4]; 7.74
[1H, dt, H6, J=7.0, 1.4]; 7.88 [1H, d, H5, J=8.0]; 7.95
[1H, s, H4]; 8.00 [1H, broad d, H8, J=8.4]; 9.29 [1H, s,
H1]. 13C NMR: 21.00 [-COCH3]; 66.31 [CHOAc]; 75.69
[-CꢀCH]; 79.72 [-CꢀCH]; 118.90 [C4]; 126.96, 127.60
and 128.02 [3C, C5, C7, C8]; 128.37 [C8a]; 130.90 [C6];
136.06 [C4a]; 148.46 [C3]; 152.97 [C1]; 169.65 [CO].
4.12.3. ( )-Acetic acid 1-(isoquinolin-3-yl)-2-methyl-
propyl ester 10c. Yield after chromatography: 85%
(colourless oil). Rf 0.52 (PE–Et2O 35:65, A). IR: wmax
2961, 1727, 1631, 1371, 1238, 1018. GC–MS: Rt 7.20;
m/z 243 (M+, 0.35); 201 (5.0); 200 (6.3); 184 (12); 183
(19); 182 (20); 168 (8.6); 167 (5.5); 159 (13); 158 (100);
143 (11); 129 (8.4); 128 (18); 102 (5.1); 77 (6.8); 43 (32).
1H NMR: 0.87 and 1.01 [6H, 2 d, -CH(CH3)2, J=7.0];
2.15 [3H, s, -COCH3]; 2.51 [1H, octuplet, -CH(CH3)2,
J=6.9]; 5.71 [1H, d, -CHOAc, J=7.4]; 7.59 [1H, ddd,
H7, J=8.0, 6.8, 1.4]; 7.62 [1H, s, H4]; 7.70 [1H, ddd, H6,
J=8.0, 7.0, 1.4]; 7.82 [1H, d, H5, J=8.0]; 7.96 [1H, dd,
H8, J=8.0, 0.8]; 9.25 [1H, s, H1]. 13C NMR: 17.88 and
18.95 [2C, -CH(CH3)2]; 21.09 [-COCH3]; 32.00
[CH(CH3)2]; 81.30 [CHOAc]; 118.43 [C4]; 126.63,
127.16 and 127.44 [3C, C5, C7, C8]; 127.91 [C8a]; 130.45
[C6]; 135.85 [C4a]; 151.87 [C3]; 152.31 [C3]; 170.56 [CO].
4.12.7. ( )-Acetic acid 1-(isoquinolin-3-yl)-3-(trimethylsi-
lyl)prop-2-ynyl ester 10g. Yield after chromatography:
90% (colourless oil). Rf 0.28 (PE–Et2O 1:1, A). IR: wmax
2962, 2232, 1742, 1629, 1368, 1251, 1229, 1048, 1017,
872. GC–MS: Rt 8.35; m/z 297 (M+, 15); 256 (10); 255
(42); 254 (100); 240 (24); 239 (8.7); 238 (26); 236 (6.1);
211 (5.4); 208 (5.7); 196 (5.0); 182 (12); 181 (6.0); 180
(20); 156 (30); 154 (5.1); 152 (6.5); 130 (5.9); 129 (11);
128 (38); 101 (5.7); 83 (5.6); 77 (8.6); 75 (12); 73 (24); 67
4.12.4. ( )-Acetic acid 1-(isoquinolin-3-yl)phenylmethyl
ester 10d. Yield after chromatography: 89%. Crystalli-
sation from Et2O–PE afforded 10d as a white solid.
Mp=75.0–75.5°C (Et2O–PE). Rf 0.20 (PE–Et2O 6:4,
A). IR: wmax 2969, 1741, 1630, 1371, 1237, 1019. GC–
MS: Rt 9.24; m/z 277 (M+, 6.4); 235 (20); 234 (100); 218
(30); 217 (42); 216 (15); 156 (7.6); 129 (12); 128 (42); 102
(5.8); 101 (5.7); 77 (17); 51 (8.3); 43 (34). 1H NMR: 2.24
[3H, s, -COCH3]; 7.07 [1H, s, CHOAc]; 7.25–7.51 [5H,
m, Ph]; 7.59 [1H, ddd, H7, J=8.0, 6.6, 1.2]; 7.70 [1H,
ddd, H6, J=8.4, 7.0, 1.4]; 7.77 [1H, s, H4]; 7.83 [1H, d,
H5, J=8.0]; 7.95 [1H, d, H8, J=8.0]; 9.22 [1H, s, H1].
13C NMR: 21.28 [-COCH3]; 77.76 [CHOAc]; 117.38
[C4]; 126.70, 127.36 and 127.50 [3C, C5, C7, C8]; 127.50
[2C, C ortho of Ph]; 127.85 [C8a]; 128.07 [C para of Ph];
128.47 [2C, C meta of Ph]; 130.59 [C6]; 136.06 [C4a];
139.20 [C ipso of Ph]; 152.40 [C3]; 152.60 [C1]; 169.95
[CO].
1
(5.5); 53 (7.8); 45 (8.4); 43 (57). H NMR: 0.20 [9H, s,
-Si(CH3)3]; 2.16 [3H, s, -COCH3]; 6.68 [1H, s, CHOAc];
7.63 [1H, dt, H7, J=7.0, 1.4]; 7.72 [1H, dt, H6, J=7.0,
1.6]; 7.86 [1H, d, H5, J=8.2]; 7.92 [1H, s, H4]; 7.99 [1H,
d, H8, J=7.6]; 9.26 [1H, s, H1]. 13C NMR: −0.25 [3C,
-Si(CH3)3]; 21.11 [-COCH3]; 66.92 [CHOAc]; 92.91
[-CꢀC-TMS]; 100.73 [-CꢀC-TMS]; 118.82 [C4]; 126.99,
127.58 and 127.86 [3C, C5, C7, C8]; 128.32 [C8a]; 130.75
[C6]; 136.10 [C4a]; 149.11 [C3]; 152.83 [C1]; 169.65 [CO].
4.12.8. ( )-Acetic acid 1-(isoquinolin-3-yl)allyl ester 10h.
Yield after chromatography: 95% (pale yellow oil). Rf
0.37 (PE–Et2O 4:6, A, B). IR: wmax 2978, 1736, 1630,
1371, 1193, 938. GC–MS: Rt 7.00; m/z 227 (M+, 2.1);
185 (8.9); 184 (55); 169 (12); 168 (100); 167 (34); 166
(7.4); 158 (7.1); 156 (10); 139 (6.9); 129 (14); 128 (29);
4.12.5. ( )-Acetic acid 1-(isoquinolin-3-yl)hex-2-ynyl
ester 10e. Yield after chromatography: 91% (orange
oil). Rf 0.35 (PE–Et2O 4:6, A, B). IR: wmax 2962, 2235,
1739, 1630, 1370, 1014, 949. GC–MS: Rt 8.66; m/z 267
(M+, 5.4); 237 (9.1); 225 (25); 224 (100); 209 (7.6); 208
(33) 206 (11); 197 (8.8); 196 (46); 195 (6.6); 193 (9.8);
192 (9.3); 182 (7.2); 181 (8.4); 180 (47); 168 (8.7); 167
(21); 166 (5.9); 156 (35); 152 (7.3); 139 (6.8); 130 (6.4);
129 (19); 128 (81); 102 (11); 101 (12); 77 (18); 76 (6.3);
1
102 (6.1); 101 (6.8); 83 (11); 51 (10); 43 (34). H NMR:
2.19 [3H, s, -COCH3]; 5.34 [1H, dt, CHꢁCHH, J=10.2,
1.3]; 5.44 [1H, dt, CꢁCHH, J=16.8, 1.4]; 6.23 [1H, ddd,
-CHꢁCH2, J=16.8, 10.2, 6.2]; 6.48 [1H, d, CHOAc,
J=6.2]; 7.61 [1H, ddd, H7, J=8.0, 6.6, 1.0]; 7.71–7.75
[1H, m, H6]; 7.72 [1H, s, H4]; 7.84 [1H, d, H5, J=8.0];
7.98 [1H, d, H8, J=8.0]; 9.27 [1H, s, H1]. 13C NMR:
21.25 [-COCH3]; 77.00 [CHOAc]; 117.83 [-CHꢁCH2];
1
75 (8.7); 63 (7.0); 51 (10); 43 (49); 39 (8.0). H NMR: