Full Paper
solid (50 %). Rf = 0.43 (EtOAc/hex, 1:2); M.p. 114–115 °C; 1H NMR
(500 MHz, CDCl3) δ = 7.99 (d, J = 8.9 Hz, 1H), 7.01 (d, J = 8.9 Hz,
1H), 6.27 (s, 1H), 3.92 (s, 3H), 3.72 (s, 3H), 1.58 (s, 6H). 13C NMR
(126 MHz, CDCl3) δ = 176.73, 173.83, 168.57, 159.08, 158.48, 142.90,
119.16, 116.24, 110.00, 88.90, 62.29, 53.20, 47.69, 23.82; IR (neat):
114.26, 110.17, 63.05, 53.15, 47.66, 29.44, 27.71, 23.90, 14.02, 10.50;
HRMS (ESI): calcd. for C27H43O5Sn [M + H+]: 567.2127, found
567.2125.
Methyl 5-Methoxy-4-oxo-6-(tributylstannyl)-4H-chromene-2-
carboxylate (21d): Prepared from corresponding aryl halide as out-
lined in Procedure B. Product obtained as a yellow oil (99 %). Rf =
0.56 (EtOAc/hex, 1:4); 1H NMR (500 MHz, CDCl3) δ = 7.68 (d, J =
8.2 Hz, 1H), 7.35 (d, J = 8.2 Hz, 1H), 7.03 (s, 1H), 4.00 (s, 3H), 3.85 (s,
3H), 1.58–1.47 (m, 6H), 1.37–1.29 (m, 6H), 1.15–1.08 (m, 6H), 0.88 (t,
J = 7.3 Hz, 9H). 13C NMR (126 MHz, CDCl3) δ = 177.80, 164.29,
161.43, 158.91, 150.54, 142.66, 133.49, 118.09, 116.82, 114.87, 63.14,
νmax = 1729, 1649, 1461, 1346, 1149, 1035, 827 cm–1; HRMS (ESI):
˜
calcd. for C15H16IO5 [M + H+]: 403.0037, found 403.0027.
Methyl
6-Iodo-5-methoxy-4-oxo-4H-chromene-2-carboxylate
(19d): Prepared from common starting material 1-(6-hydroxy-3-
iodo-2-methoxy)-acetophenone and the corresponding diester as
outlined in Procedure A. Product obtained as a white solid (86 %).
Rf = 0.27 (EtOAc/hex, 1:4); M.p. 153–155 °C; 1H NMR (500 MHz,
CDCl3) δ = 8.07 (d, J = 9.0 Hz, 1H), 7.19 (d, J = 8.9 Hz, 1H), 7.04 (s,
1H), 4.00 (s, 3H), 3.92 (s, 3H). 13C NMR (126 MHz, CDCl3) δ = 176.45,
161.04, 159.17, 158.00, 150.87, 143.91, 120.11, 116.88, 116.46, 89.87,
53.77, 29.42, 27.69, 14.01, 10.56; IR (neat): νmax = 2924, 1745, 1656,
˜
1404, 1359, 1253, 1108, 1045, 873, 774 cm–1; HRMS (ESI): calcd. for
C24H37O5Sn [M + H+]: 525.1657, found 525.1656.
5-Methoxy-2-(tetrahydrofuran-2-yl)-6-(tributylstannyl)-4H-
chromen-4-one (21e): Prepared from corresponding aryl halide as
outlined in Procedure B. Product obtained as yellow oil (87 %). Rf =
0.67 (EtOAc/Hex, 2:3); 1H NMR (500 MHz, [D]Chloroform) δ = 7.58
(d, J = 8.1 Hz, 1H), 7.17 (d, J = 8.2, 1.4 Hz, 1H), 6.33 (s, 1H), 4.77 (dd,
J = 8.0, 5.1 Hz, 1H), 4.10–3.91 (m, 2H), 3.84 (s, 3H), 2.39–2.06 (m,
2H), 2.03–1.98 (m, 2H), 1.54–1.49 (m, 5H), 1.37–1.28 (m, 7H), 1.13–
1.07 (m, 5H), 0.90–0.85 (m, 9H); 13C NMR (126 MHz, [D]Chloroform)
δ = 178.00, 167.44, 164.45, 159.43, 141.49, 132.26, 114.34, 109.64,
76.96, 69.76, 63.11, 31.35, 29.57, 29.49, 29.41, 27.75, 25.77, 10.55; IR
62.37, 53.90; IR (neat): νmax = 1731, 1639, 1409, 1368, 1258, 1125,
˜
1041, 840, 770 cm–1; HRMS (ESI): calcd. for C12H10IO5 [M + H+]:
360.9567, found 360.9551.
6-Iodo-5-Methoxy-2-(tetrahydrofuran-2-yl)-4H-chromen-4-one
(19e): Prepared from common starting material 1-(6-hydroxy-3-
iodo-2-methoxy)-acetophenone and the corresponding diester as
outlined in Procedure A. Product obtained as yellow solid (74 %).
1
Rf = 0.36 (EtOAc/Hex, 2:3); M.p. 94–95 °C; H NMR (500 MHz CDCl3)
δ = 7.98 (d, J = 8.9 Hz, 1H), 7.02 (d, J = 8.9 Hz, 1H), 6.36 (d, J =
0.9 Hz, 1H), 4.80–4.73 (m, 1H), 4.10–4.04 (m, 1H), 3.99–3.93 (m, 1H),
3.91 (s, 3H), 2.42–2.29 (m, 1H), 2.14–2.05 (m, 1H), 2.05–1.97 (m, 2H);
13C NMR (126 MHz, [D]Chloroform) δ = 176.37, 167.73, 159.02,
158.30, 142.54, 119.47, 116.09, 109.17, 88.73, 76.59, 69.57, 62.12,
(neat): νmax = 2923, 1656, 1402, 1321, 1050, 862 cm–1; HRMS (ESI):
˜
calcd. for C26H40O4Sn[M + H+]: 537.1949, found 537.2004.
Dimethyl 4,4′-(5,5′-Dimethoxy-4,4′-dioxo-4H,4′H-[6,6′-bichrom-
ene]-2,2′-diyl)dibutyrate (22a): Prepared from corresponding aryl
stannane as outlined in the Procedure C. Product obtained as a
white solid (28 %). Rf = 0.59 (EtOAc/hex, 2:1); M.p. 57–58 °C; 1H NMR
(500 MHz, CDCl3) δ = 7.61 (d, J = 9.0 Hz, 1H), 7.16 (d, J = 9.0 Hz,
1H), 6.10 (s, 1H), 3.96 (s, 3H), 3.69 (s, 3H), 2.64 (t, J = 7.6 Hz, 2H),
2.43 (t, J = 7.3 Hz, 2H), 2.06 (p, J = 7.3 Hz, 2H). 13C NMR (126 MHz,
CDCl3) δ = 176.87, 173.36, 166.94, 156.82, 155.45, 134.28, 125.30,
119.81, 115.02, 111.74, 62.20, 52.08, 33.24, 33.15, 22.12; IR (neat):
31.12, 25.54; IR (neat): νmax = 2930, 1657, 1431, 1329, 1044, 856,
˜
787 cm–1; HRMS (ESI): calcd. for C14H13IO4 [M + H+]: 372.9859, found
372.9915.
Methyl 4-[5-Methoxy-4-oxo-6-(tributylstannyl)-4H-chromen-2-
yl]butanoate (21a): Prepared from corresponding aryl halide as
outlined in Procedure B. Product obtained as a colorless oil (96 %).
Rf = 0.22 (EtOAc/hex, 1:4); 1H NMR (500 MHz, CDCl3) δ = 7.59 (d, J =
8.2 Hz, 1H), 7.17 (d, J = 8.1 Hz, 1H), 6.10 (s, 1H), 3.85 (s, 3H), 3.69 (s,
3H), 2.63 (t, J = 7.5 Hz, 2H), 2.43 (t, J = 7.3 Hz, 2H), 2.10–2.03 (m,
2H), 1.57–1.47 (m, 6H), 1.38–1.27 (m, 6H), 1.14–1.07 (m, 6H), 0.88 (t,
J = 7.3 Hz, 9H). 13C NMR (126 MHz, CDCl3) δ = 177.82, 173.47,
166.34, 164.32, 159.55, 141.38, 132.13, 117.26, 114.25, 112.00, 63.06,
52.05, 33.27, 33.22, 29.44, 27.71, 22.21, 14.02, 10.50; HRMS (ESI):
calcd. for C27H43O5Sn [M + H+]: 567.2127, found 567.2125.
ν
= 1741, 1642, 1408, 1341, 1296, 1143, 1041, 882, 751 cm–1
;
˜
max
calcd. for [M + H+]: 560.1839.
Dimethyl 3,3′-(5,5′-Dimethoxy-4,4′-dioxo-4H,4′H-[6,6′-bichrom-
ene]-2,2′-diyl)dipropionate (22b): Prepared from corresponding
aryl stannane as outlined in the Procedure C. Product obtained as
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a white solid (26 %). Rf = 0.33 (EtOAc/hex, 1:1); M.p. 112–113 °C; H
NMR (500 MHz, CDCl3) δ = 7.61 (d, J = 9.0 Hz, 1H), 7.15 (d, J =
9.0 Hz, 1H), 6.11 (s, 1H), 3.96 (s, 3H), 3.72 (s, 3H), 2.93 (t, J = 7.3 Hz,
2H), 2.74 (t, J = 7.3 Hz, 2H). 13C NMR (126 MHz, CDCl3) δ = 176.77,
172.21, 165.93, 156.73, 155.46, 134.33, 125.38, 119.80, 114.95,
Methyl 3-[5-Methoxy-4-oxo-6-(tributylstannyl)-4H-chromen-2-
yl]propanoate (21b): Prepared from corresponding aryl halide as
outlined in Procedure B. Product obtained as a colorless oil (95 %).
Rf = 0.22 (EtOAc/hex, 1:4); 1H NMR (500 MHz, CDCl3) δ = 7.59 (d, J =
8.2 Hz, 1H), 7.16 (d, J = 8.2 Hz, 1H), 6.12 (s, 1H), 3.84 (s, 3H), 3.72 (s,
3H), 2.92 (t, J = 7.5 Hz, 2H), 2.75 (t, J = 7.4 Hz, 2H), 1.57–1.47 (m,
6H), 1.38–1.27 (m, 6H), 1.14–1.06 (m, 6H), 0.88 (t, J = 7.3 Hz, 9H).
13C NMR (126 MHz, CDCl3) δ = 177.74, 172.39, 165.33, 164.33,
159.47, 141.45, 132.25, 117.25, 114.17, 111.79, 63.06, 52.37, 31.08,
29.44, 29.23, 27.70, 14.02, 10.50; HRMS (ESI): calcd. for C26H41O5Sn
[M + H+]: 553.1970, found 553.1970.
111.56, 62.19, 52.40, 30.93, 29.16; IR (neat): νmax = 1736, 1647, 1409,
˜
1367, 1295, 1176, 1056, 830, 790 cm–1; calcd. for [M + H+]: 523.1526.
Dimethyl 2,2′-(5,5′-Dimethoxy-4,4′-dioxo-4H,4′H-[6,6′-bichrom-
ene]-2,2′-diyl)bis(2-methylpropanoate) (22c): Prepared from cor-
responding aryl stannane as outlined in the Procedure C Product
obtained as a white solid (24 %). Rf = 0.50 (EtOAc/hex, 1:2); M.p.
1
109–110 °C; H NMR (500 MHz, CDCl3) δ = 7.62 (d, J = 9.0 Hz, 1H),
7.16 (d, J = 9.0 Hz, 1H), 6.25 (s, 1H), 3.97 (s, 3H), 3.72 (s, 3H), 1.58 (s,
6H). 13C NMR (126 MHz, CDCl3) δ = 177.15, 173.86, 168.63, 156.65,
155.40, 134.51, 125.40, 119.66, 115.03, 110.00, 62.20, 53.20, 47.68,
Methyl 2-[5-Methoxy-4-oxo-6-(tributylstannyl)-4H-chromen-2-
yl]-2-methylpropanoate (21c): Prepared from corresponding aryl
halide as outlined in Procedure B. Product obtained as a colorless
23.84; IR (neat): νmax = 1733, 1651, 1407, 1350, 1255, 1152, 1045,
˜
822 cm–1; calcd. for [M + H+]: 551.1839.
1
oil (95 %). Rf = 0.47 (EtOAc/hex, 1:4); H NMR (500 MHz, CDCl3) δ =
7.59 (d, J = 8.2 Hz, 1H), 7.17 (d, J = 8.2 Hz, 1H), 6.26 (s, 1H), 3.86 (s,
Dimethyl 5,5′-Dimethoxy-4,4′-dioxo-4H,4′H-[6,6′-bichromene]-
2,2′-dicarboxylate (22d): Prepared from corresponding aryl
3H), 3.72 (s, 3H), 1.58 (s, 6H), 1.54–1.48 (m, 7H), 1.37–1.29 (m, 6H),
1.14–1.07 (m, 6H), 0.88 (t, J = 7.3 Hz, 9H). 13C NMR (126 MHz, CDCl3) stannane as outlined in the Procedure C. Product obtained as a
δ = 178.09, 174.13, 168.09, 164.28, 159.39, 141.63, 132.25, 117.12,
white solid (35 %). Rf = 0.21 (EtOAc/hex, 1:4); M.p. 151–153 °C;
Eur. J. Org. Chem. 0000, 0–0
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