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A. Mohamed-Hachi et al.
PAPER
overall yields of the synthesis of aromatic dienals 2a–c,
calculated from 3d.
Table 3 Comparative Overall Yields of the Synthesis of 2a–c
from 3d
Except for 2a, for which the direct method is slighly bet-
ter, the indirect routes allow the yields to increase by more
than 10%.
Product
Direct routea
via 5ab
via 5bb
2a
2b
2c
62
51
48
58.5
65.5
63.1
59.8
62.3
63.9
In summary, the above examples illustrate the effective-
ness of the dienolates of (E)-4-diethoxyphosphonyl-2-me-
thylbut-2-enal as stereoselective polyvinologation
reagents of aldehydes, especially when they are in situ
a Conditions of Entry 5, Table 1.
b Calculated yield.
Table 4 1H and 13C NMRa and MS Data of Compounds 5 and 2
Prod- 1H NMR (CDCl3 / TMS)
13C{1H}NMR (CDCl3 / TMS)
d, J (Hz)
MS (70 eV)
m / z (%)
uct
d, J (Hz)
5ab
1.3 (t, J = 7, 6 H, CH3CH2O), 1.73 (s, 3 H,
9.6 (CH3C-2), 16.2 (d, J = 6.3, CH3CH2O), 262 (M+., 6), 220 (55), 192 (40), 175
CH3C-2), 2.21 (s, 3 H, CH3C=O), 4.10 (q,
20.5 (CH3C=O), 61.6 (d, J = 5.7,
J = 7, 4 H, CH3CH2O), 5.71 (t, J = 17.5, 1 H, CH3CH2O), 112.6 (d, J = 195.5, C-4),
(6), 164 (11), 138 (51), 124 (24), 111
(32), 97 (28), 82 (38), 65 (17), 53 (22),
H-4), 7.05 (dd, J = 21.9, 17.5, 1 H, H-3), 7.51 119.3 (d, J = 24.6, C-2), 140.8 (C-1), 148.1 43 (100), 37 (10)
(s, 1 H, H-1). (d, J = 7.3, C-3), 166.9 (C=O).
5bc
1.05 (d, J = 5.3, 18 H, CH3CH-Si), 1.10–1.25 8.4 (CH3C-2), 11.5 (CH3CHSi), 16.1 (d,
376 (M+., 10), 333 (100), 305 (11), 277
(m, 3 H, CH3CHSi), 1.31 (t, J = 7, 6 H,
CH3CH2O), 1.72 (s, 3 H, CH3C-2), 4.10 (q,
J = 6.5, CH3CH2O), 17.3 (CH3CHSi), 61.0 (23), 259 (63), 233 (19), 217 (8), 203
(d, J = 5.3, CH3CH2O), 106.1 (d, J = 194.9, (5), 173 (6), 151 (6), 125 (8), 75 (8), 59
J = 7, 4 H, CH3CH2O), 5.41 (dd, J = 18.9, 16.9, C-4), 117.1 (d, J = 24.0, C-2), 149.1 (C-1), (19), 45 (8)
1 H, H-4), 6.81 (s, 1 H, H-1), 7.15 (dd, J = 22.1, 150.5 (d, J = 7.9, C-3).
16.9, 1 H, H-3).
d
2a
2b
2c
–
–
9.5 (CH3C-2), 123.2 (C-4), 127.3 (Co-arom), 172 (M+., 78), 157 (14), 143 (28), 141
128.7 (Cm-arom), 129.3 (C-5), 135.9 (Ci-arom), (14), 129 (100), 115 (49), 104 (24), 91
137.5 (C-2), 141.0 (Cp-arom), 148.5 (C-3), (21), 77 (18), 65 (18), 63 (21), 51 (24),
194.5 (C-1).
39 (28)
e
9.5 (CH3C-2), 112.3 (C-4’-fur), 112.7,
162 (M+., 100), 147 (13), 133 (41), 119
(C-3’-fur), 121.6 (C-4), 127.2 (C-5), 137.5 (35), 115 (13), 105 (69), 94 (70), 77
(C-2), 144.1 (C-5’-fur), 148.1 (C-3), 152.2 (69), 66 (26), 51 (57), 39 (57)
(C-2’-fur), 194.3 (C-1).
1.89 (s, 3 H, CH3C-2), 6.91 (d, J = 15.5, 1 H, H- 9.1 (CH3C-2), 123.2 (C-4), 124.8 (C-5),
5), 6.95 (d, J = 11, 1 H, H-3), 7.22 (dd, 131.3 (C-3’-pyr), 132.9 (C-4’-pyr), 136.4 (76), 128 (6), 117 (26), 105 (21), 95
173 (M+., 85), 158 (16), 144 (100), 130
J = 15.5, 11, 1 H, H-4), 7.25 (dd, J = 8, 4.7, 1 H, (C-5’-pyr), 138.1 (C-2), 147.1 (C-3), 148.6 (21), 77 (15), 63 (31), 51 (35), 39 (44)
H-5’-pyr), 7.75 (dt, J = 8, 1.9, 1 H, H-4’-pyr), (C-2’-pyr), 149.3 (C-6’-pyr), 193.9 (C-1).
8.48 (dd, J = 4.7, 1.4, H-6’-pyr), 8.66 (d,
J = 1.9, 1 H, H-2’-pyr), 9.46 (s, 1 H, H-1).
2d
2,f
1.91 (s, 3 H, CH3C-2), 6.75–7.00 (m, 5 H,
Halkene), 7.25–7.60 (m, 5 H, Harom), 9.48 (s, 1 H, 128.9, 137.4 (C-4, C-5, C-6, C-7), 128.7
H-1).
9.5 (CH3C-2), 126.8 (Co-arom), 127.5, 128.1, 198 (M+., 100), 197 (21), 183 (19), 169
(34), 155 (48), 129 (46), 115 (57), 104
(Cm-arom), 136.3 (Ci-arom), 137.2 (C-2), 141.4 (17), 91 (91), 77 (29), 65 (23), 51 (20),
(Cp-arom), 148.3 (C-3), 194.3 (C-1).
39 (30)
0.78 (d, J = 6.7, 6 H, CH3CH), 1.6 (m, 1 H,
8.9 (CH3C-2), 21.9 (CH3CH), 27.9
152 (M+., 9), 134 (2), 123 (2), 110 (3),
CH3CH), 1.69 (s, 3 H, CH3C-2), 1.89 (t, J = 7, (CH3CH), 42.3 (CH2), 126.5 (C-4), 135.5 109 (6), 95 (100), 81 (17), 67 (21), 65
2 H, CH2), 6.0 (m, 1 H, H-5), 6.36 (dd, J = 15, (C-2), 144.3 (C-5), 148.8 (C-3), 194.7
11, 1 H, H-4), 6.69 (d, J = 11, 1 H, H-3), 9.27 (C-1).
(s, 1 H, H-1).
(5), 53 (9), 41 (32), 34 (2)
2ff
0.85 (t, J = 7, 3 H, CH3CH2), 1.2 [m, 4 H,
8.3 (CH3C-2), 21.5 (CH3CH2), 27.4
166 (M+., 13), 109 (5), 95 (100), 81
(10), 67 (16), 53 (8), 41 (20)
CH3(CH2)2], 1.4 [m, 2 H, CH3(CH2)2CH2], 1.78 (CH3CH2CH2), 30.4 [CH3(CH2)2CH2],
(s, 3 H, CH3C-2), 2.15 (m, 2 H, CH2C-5), 6.2 32.4 (CH2C-5), 124.8 (C-4), 134.9 (C-2),
(m, 1 H, H-5), 6.47 (dd, J = 13, 11, 1 H, H-4), 145.0 (C-5), 148.4 (C-3), 194.2 (C-1).
6.8 (d, J = 11, 1 H, H-3), 9.37 (s, 1 H, H-1).
a For numbering of the carbon atoms of the dienic chain, see Scheme 2.
b 31P NMR: d (CDCl3) = 17.7.
c 31P NMR: d (CDCl3) = 20.6.
d Data in full agrement with Refs. 18 and 19.
e Data in full agrement with Ref. 18.
f Data refer to the major isomer.
Synthesis 1999, No. 7, 1188–1192 ISSN 0039-7881 © Thieme Stuttgart · New York