10
S. Chassaing et al. / Tetrahedron xxx (2014) 1e13
4
4
13
J¼2.2 Hz), 7.36 (1H, d, J¼2.2 Hz), 7.42e7.48 (2H, m), 7.95 (1H, s),
(1H, s), 7.44 (1H, s), 7.61e7.73 (3H, m), 8.11e8.15 (4H, m). d C NMR
(75 MHz, CD CN/1% TFA-d 158.1, 157.6, 157.1, 157.0, 156.9, 156.5,
13
8
.36e8.40 (2H, m). d C NMR (75 MHz, CD
3
CN/1% TFA-d
1
)
d
175.3,
3
1
) d
1
9
72.0, 168.7, 167.2, 160.4, 158.8, 131.4, 120.4, 117.1, 114.7, 109.1, 103.4,
153.4, 151.6, 134.1, 130.2, 129.5, 127.4, 120.4, 115.2,112.8, 102.5,101.4,
þ
6.1, 25.2. dm/z (ESI, positive mode) 271 (100%, M ). dHRMS (ESI,
100.6, 100.4, 55.7. dm/z (ESI, positive mode) 396 (100), 369 (50%,
þ
þ
þ
positive mode) M found 271.0745; C16FH12
O
3
requires 271.0765.
15 4
M ). dHRMS (ESI, positive mode) M found 369.1150; C17H O
requires 369.1121.
0
0
0
4
2
.6.5. 5,7-Dihydroxy-3-(3 ,4 ,5 -trimethoxybenzoyloxy)-4-methyl-
-phenyl-benzopyrylium hexafluorophosphate hexafluorophos-
4.7.3. 8-Hydroxy-5-phenyl-2-(4-(N,N)-dimethylamino)phenyl-1,6-
dioxaphenalene hexafluorophosphate 3ac (Scheme 6dprepared via
condensation of 6a and 4-(N,N)-dimethylaminobenzaldehy-
phate 6h (Scheme 5dprepared via condensation of phloroglucinol
8
>
and
a
-aroylacetone 7h). Orange solid. dYield 24%. dmp
260 C. dIR (KBr) max 3354 (OeH), 1695 (C]O), 1644 (C]O),
max (ε) 386
20,100), 464 (13,100) nm (L mol cm ). d H NMR (300 MHz,
CD CN/1% TFA-d 3.01 (3H, s), 3.87 (3H, s), 3.92 (6H, s), 6.88
ꢁ
ꢁ
n
de). Purple solid. dYield 83%. dmp >260 C. dUV/Vis (MeOH/5%
ꢀ1
ꢀ1
ꢀ1
1
8
(
52 (PeF) cm . dUV/Vis (MeOH/5% 1 M HCl)
l
1 M HCl)
(300 MHz, CD
l
max (ε) 260, 552 (44,200) nm (L mol cm ). d H NMR
ꢀ1
ꢀ1
1
4
3
CN/1% TFA-d
1
)
d
3.28 (6H, s), 7.26 (1H, d, J¼2.0 Hz),
4
3
1
)
d
7.28 (1H, d, J¼2.0 Hz), 7.52 (1H, s), 7.55 (1H, s), 7.56e7.61 (2H, m),
4
4
(
(
(
1
1
1H, d, J¼2.2 Hz), 7.11 (1H, d, J¼2.2 Hz), 7.49 (2H, s), 7.59e7.64
7.67e7.71 (2H, m), 7.74e7.80 (1H, m), 8.17e8.21 (2H, m), 8.25e8.29
13
þ
2H, m), 7.70e7.73 (1H, m), 8.19e8.24 (2H, m). d C NMR
75 MHz, CD CN/1% TFA-d 169.6, 166.5, 163.2, 160.9, 158.4,
53.6, 144.2, 134.7, 129.8, 129.6, 127.8, 125.6, 125.3, 124.8, 113.6,
07.9, 104.2, 96.3, 60.1, 56.1, 17.7. dm/z (ESI, positive mode) 463
(2H, m). dm/z (ESI, positive mode) 382 (100%, M ). dHRMS (ESI,
þ
3
1
)
d
positive mode) M found 382.1443; C25
H
20NO
3
requires 382.1443.
4.7.4. 8-Hydroxy-5-phenyl-2-(3,4,5-trimethoxyphenyl)-1,6-
dioxaphenalene hexafluorophosphate 3ad (Scheme 6dprepared via
condensation of 6a and 3,4,5-trimethoxybenzaldehyde). Purple
þ
þ
(
100%, M ). dHRMS (ESI, positive mode) M found 463.1393;
requires 463.1387.
26 23 8
C H O
ꢁ
solid. dYield 79%. dmp >260 C. dUV/Vis (MeOH/5% 1 M HCl)
ꢀ1 ꢀ1
1
4.6.6. 7-Hydroxy-4-methyl-2-phenyl-benzopyrylium
hexa-
lmax (ε) 386 (11,700), 494 (38,700) nm (L mol cm ). d H NMR
4
fluorophosphate 15 (Table 1dprepared via condensation of resorcinol
and
(300 MHz, CD
3
CN/1% TFA-d
1
)
d
3.97 (9H, s), 7.19 (1H, d, J¼2.2 Hz),
4
a
-aroylacetone 7a). Yellow solid. dYield 73%. dmp
7.24 (1H, d, J¼2.2 Hz), 7.40 (1H, s), 7.43 (2H, s), 7.49 (1H, s),
ꢁ
13
2
12e215 C. dIR (KBr)
n
max 3072 (OeH), 1630 (C]O), 1461, 1371,
max (ε) 292
12,000), 416 (28,600) nm (L mol cm ). d H NMR (300 MHz,
7.61e7.66 (2H, m), 7.70e7.72 (1H, m), 8.12e8.15 (2H, m). d C NMR
ꢀ
1
1239, 858 (PeF) cm . dUV/Vis (MeOH/5% 1 M HCl)
l
3 1
(75 MHz, CD CN/1% TFA-d ) d 158.1, 157.6, 157.0, 156.5, 153.3, 151.2,
ꢀ
1
ꢀ1
1
(
148.1, 134.0,129.5,127.4, 120.4,119.9, 112.8, 109.1, 105.5,102.3,101.8,
3
þ
CD
3
CN/1% TFA-d
1
)
d
3.03 (3H, s), 7.49 (1H, dd, J¼9.1 Hz &
100.6, 100.5, 56.2, 56.0. dm/z (ESI, positive mode) 415 (100%, M ).
4
4
þ
J¼2.2 Hz), 7.56 (1H, d, J¼2.2 Hz), 7.68e7.75 (2H, m), 7.79e7.85
dHRMS (ESI, positive mode) M found 415.1231; C26
H
21
O
6
requires
3
(1H, m), 8.30 (1H, s), 8.33 (1H, d, J¼9.1 Hz), 8.35e8.39 (2H, m).
d
415.1176.
13
3 1
C NMR (75 MHz, CD CN/1% TFA-d ) d 158.1, 157.6, 157.0, 156.5,
1
35.9,130.0, 129.5, 129.0, 128.9, 121.6, 120.4, 115.4, 102.9, 20.1. dm/z
4.7.5. 8-Hydroxy-2,5-di(4-methoxyphenyl)-1,6-dioxaphenalene
hexafluorophosphate 3bb (Scheme 6dprepared via condensation
þ
(
ESI, positive mode) 237 (100%, M ).
of 6b and p-methoxybenzaldehyde). Red solid. dYield 77%. dmp
ꢁ
4
.7. General procedure for the condensation of 4-
>260 C. dUV/Vis (MeOH/5% 1 M HCl)
l
max (ε) 374 (12,100), 482
cm ). d H NMR (300 MHz, CD CN/1%
3.93 (6H, s), 7.15 (2H, s), 7.15e7.18 (4H, m), 7.35 (2H, s),
ꢀ1
ꢀ1
1
methylflavylium salts 6aec,e,h with benzaldehydes (Scheme 6
and Table 1)
(18,400) nm (L mol
TFA-d
3
1
)
d
13
8
3 1
.10e8.14 (4H, m). d C NMR (75 MHz, CD CN/1% TFA-d )
Benzaldehyde (1.2 equiv) was added to a solution of 4-
methylflavylium hexafluorophosphate 6aec,e,h (1.0 equiv) in
a minimum of EtOH. The solution was heated at reflux and moni-
tored by UVevis spectrophotometry. When complete conversion
was observed (24 h heating generally needed), the reaction mixture
was cooled to room temperature and EtOH was evaporated under
vacuum. The resulting residue was finally washed with Et O to give
2
the expected pyranoflavylium salts 3 (Scheme 8) or 4-styrylated
flavylium salts 16/17 (Table 1) in pure forms.
d
163.7, 162.6, 148.8, 139.2, 134.2, 130.7, 116.1, 109.7, 104.3, 102.3,
þ
101.5, 56.7. dm/z (ESI, positive mode) 399 (100%, M ). dHRMS
(ESI, positive mode) M found 399.1235; C25
399.1227.
þ
19 5
H O requires
4.7.6. 8-Hydroxy-5-(4-methoxyphenyl)-2-(4-(N,N)-dimethylamino)
phenyl-1,6-dioxaphenalene hexafluorophosphate 3bc (Scheme
6dprepared via condensation of 6b and 4-(N,N)-dimethylamino-
ꢁ
benzaldehyde). Green solid. dYield 83%. dmp >260 C. dUV/Vis
ꢀ
1
ꢀ1
1
(MeOH/5% 1 M HCl)
l
max (ε) 565 (42,300) nm (L mol cm ). d H
4
.7.1. 8-Hydroxy-5-phenyl-2-(4-hydroxyphenyl)-1,6-dioxaphenalene
NMR (300 MHz, CD
3
CN/1% TFA-d 3.29 (6H, s), 3.91 (3H, s),
1
) d
4
4
hexafluorophosphate 3aa (Scheme 6dprepared via condensation of
6
7.09e7.12 (2H, m), 7.16 (1H, d, J¼2.2 Hz), 7.18 (1H, d, J¼2.2 Hz),
a and p-hydroxybenzaldehyde). Purple solid. dYield 75%. dmp
7.41 (1H, s), 7.43 (1H, s), 7.69e7.72 (2H, m), 8.08e8.12 (2H, m),
ꢁ
13
>
260 C. dUV/Vis (MeOH/5% 1 M HCl)
l
max (ε) 374 (8300), 452
8.21e8.24 (2H, m). d C NMR (75 MHz, CD
158.1, 157.6, 157.1, 157.0, 156.5, 154.1, 151.0, 130.0, 129.7, 120.4, 115.2,
3
CN/1% TFA-d
1
)
d
165.9,
ꢀ1
ꢀ1
1
(
10,500) nm (L mol cm ). d H NMR (300 MHz, CD
3
CN/1% TFA-
4
d
1
)
d
7.07e7.11 (2H, m), 7.23 (1H, d, J¼2.2 Hz), 7.25 (1H, d,
112.8,109.1,102.2,101.4,100.4, 55.7, 44.2. dm/z (ESI, positive mode)
4
þ
þ
J¼2.2 Hz), 7.67 (1H, s), 7.65e7.69 (2H, m), 7.70 (1H, s), 7.72e7.78
412 (100%, M ). dHRMS (ESI, positive mode) M found 412.1568;
requires 412.1543.
(
1H, m), 8.11e8.14 (2H, m), 8.15e8.19 (2H, m). dm/z (ESI, positive
26 4
C H22NO
þ
þ
mode) 355 (100%, M ). dHRMS (ESI, positive mode) M found
3
55.0968; C17
H
15
O
4
requires 355.0965.
4.7.7. 8-Hydroxy-5-(3,4,5-trimethoxyphenyl)-2-(4-hydroxyphenyl)-
,6-dioxaphenalene hexafluorophosphate 3ca (Scheme 6dprepared
1
4
. 7. 2. 8-Hydroxy-5-phenyl-2-(4-methoxyphenyl)-1, 6-
via condensation of 6c and p-hydroxybenzaldehyde). Red solid.
ꢁ
dioxaphenalene hexafluorophosphate 3ab (Scheme 6dprepared via
condensation of 6a and p-methoxybenzaldehyde). Red solid. dYield
8
dYield 65%. dmp >260 C. dUV/Vis (MeOH/5% 1 M HCl)
260, 486 (38,900) nm (L mol cm ). d H NMR (300 MHz, CD
l
max (ε)
3
CN/
ꢀ1
ꢀ1
1
ꢁ
0%. dmp >260 C. dUV/Vis (MeOH/5% 1 M HCl)
lmax (ε) 372
1% TFA-d 3.89 (3H, s), 3.97 (6H, s), 7.05e7.08 (2H, m), 7.19 (1H, d,
1
) d
ꢀ1
ꢀ1
1
4
4
(
22,400), 478 (10,500) nm (L mol cm ). d H NMR (300 MHz,
J¼2.2 Hz), 7.24 (1H, d, J¼2.2 Hz), 7.34 (1H, s), 7.40 (2H, s), 7.49 (1H,
13
CD CN/1% TFA-d 3.92 (3H, s), 7.13e7.16 (2H, m), 7.29 (2H, s), 7.41
3
1
)
d
s), 8.07e8.10 (2H, m). d C NMR (75 MHz, CD
3 1
CN/1% TFA-d )