UPDATES
Copper-Promoted Coupling of Carbon Dioxide
ethyl ether (30 mL) and then filtered. The volatile com-
pounds were removed under vacuum and the crude product
was purified by column chromatography on a silica gel
column using petroleum ether/ethyl acetate as eluent to give
the desired product.
CDCl3) d=8.63 (d, J=3.1 Hz, 1H), 7.67–7.58 (m, 2H), 7.17
(t, J=5.9 Hz, 1H), 2.86–2.81 (m, 2H), 2.18–2.14 (m, 2H),
2.05–1.92 (m, 4H); 13C NMR (100 MHz, CDCl3) d=154.3,
149.6, 149.2, 148.8, 136.5, 123.7, 123.2, 97.0, 72.8, 37.5, 25.2;
MS (EI, 70 eV): m/z (%)=357m+], 313, 272 (100), 244, 216,
158, 90, 63; HRMS-ESI (m/z): calcd for C13H13INO3 (M+
H)+: 357.9935; found: 357.9947.
(E)-5-(Iodo(pyridin-2-yl)methylene)-4,4-dimethyl-1,3-di-
oxolan-2-one (3a): pale yellow solid; mp: 113–1158C; IR
(KBr): 2924, 1813, 1660, 1277, 1028, 766 cmÀ1 1H NMR
;
(E)-5-(Iodo(6-methylpyridin-2-yl)methylene)-4,4-dimeth-
yl-1,3-dioxolan-2-one (3g): yellow solid; mp: 107–1088C; IR
(400 MHz, CDCl3): d=8.65 (s, 1H), 7.65 (t, J=7.6 Hz, 1H),
7.57 (d, J=8.0 Hz, 1H), 7.18 (t, J=6.4 Hz, 1H), 1.97 (s,
6H); 13C NMR (100 MHz, CDCl3): d=154.3, 150.8, 149.4,
149.3, 136.4, 123.6, 123.3, 87.5, 72.7, 25.1; MS (EI, 70 eV):
m/z (%)=331 [M+], 287 (100), 258, 217, 160, 117, 90, 63;
HRMS-ESI (m/z): calcd for C11H11INO3 (M+H)+: 331.9778;
found: 331.9781.
(KBr): 2961, 1823, 1650, 1279, 1074, 788 cmÀ1 1H NMR
;
(400 MHz, CDCl3): d=7.54 (t, J=7.6 Hz, 1H), 7.32 (d, J=
7.6 Hz, 1H), 7.04 (d, J=7.6 Hz, 1H), 2.57 (s, 3H), 1.97 (s,
6H); 13C NMR (100 MHz, CDCl3) d=158.3, 153.7, 150.3,
149.3, 136.5, 122.9, 120.5, 87.3, 72.7, 25.1, 24.5; MS (EI,
70 eV): m/z (%)=345m+], 301, 272, 260, 174, 146, 131(100),
104, 77; HRMS-ESI (m/z): calcd for C12H13INO3 (M+H)+:
345.9948; found: 345.9935.
(E)-4-Ethyl-5-(iodo(pyridin-2-yl)methylene)-4-methyl-1,3-
dioxolan-2-one (3b): yellow solid; mp: 107–1088C; IR
(KBr): 2977, 1824 1649, 1269, 1045, 767 cmÀ1 1H NMR
;
(E)-5-(Iodo(6-methoxypyridin-2-yl)methylene)-4,4-di-
methyl-1,3-dioxolan-2-one (3h): yellow solid; mp: 98–998C;
IR (KBr): 2982, 2920, 1822, 1647, 1581, 1464, 1260, 1148,
(400 MHz, CDCl3): d=8.65 (s, 1H), 7.66 (td, J=7.6, 1.6 Hz,
1H), 7.58 (d, J=8.0 Hz, 1H), 7.18 (dd, J=6.4, 5.2 Hz, 1H),
2.63–2.53 (m, 1H), 2.09–1.99 (m, 1H), 1.95 (s, 3H), 1.04 (t,
J=7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=154.3,
149.6, 149.5, 149.4, 136.4, 123.6, 123.3, 90.6, 73.3, 30.2, 23.9,
7.4; MS (EI, 70 eV): m/z (%)=345 [M+], 273 (100), 245,
146, 90; HRMS-ESI (m/z): calcd for C12H13INO3 (M+H)+:
345.9935; found: 345.9940.
1
1074, 1026, 799 cmÀ1; H NMR (400 MHz, CDCl3): d=7.55
(t, J=8.0 Hz, 1H), 7.28 (s, 1H), 6.65 (d, J=8.0 Hz, 1H),
3.98 (s, 3H), 2.00 (s, 6H); 13C NMR (100 MHz, CDCl3): d=
163.2, 150.7, 150.3, 149.5, 138.9, 116.3, 110.6, 87.73, 75.2,
53.6, 25.2; MS (EI, 70 eV): m/z (%)=361m+], 317, 162, 147
(100), 77; HRMS-ESI (m/z): calcd for C12H13INO4 (M+H)+:
361.9883; found: 361.9884.
(E)-4,4-Diethyl-5-(iodo(pyridin-2-yl)methylene)-1,3-diox-
olan-2-one (3c): yellow solid; mp: 137–1388C; IR (KBr):
(E)-5-((6-Fluoropyridin-2-yl)iodomethylene)-4,4-dimeth-
yl-1,3-dioxolan-2-one (3i): yellow solid; mp: 130–1328C; IR
1
2973, 1815, 1651, 1264, 1056, 765 cmÀ1; H NMR (400 MHz,
CDCl3) d=8.66 (d, J=4.0 Hz, 1H), 7.65 (td, J=7.7, 1.7 Hz,
1H), 7.58 (d, J=7.9 Hz, 1H), 7.18 (dd, J=6.5, 5.0 Hz, 1H),
2.62–2.53 (m, 2H), 2.05–1.94 (m, 2H), 1.05 (t, J=7.4 Hz,
6H); 13C NMR (100 MHz, CDCl3): d=154.2, 149.8, 149.4,
148.1, 136.4, 123.5, 123.2, 94.1, 74.3, 29.1, 7.2; MS (EI,
70 eV): m/z (%)=359m+], 315, 287, 245 (100), 90; HRMS-
ESI (m/z): calcd for C13H15INO3 (M+H)+: 360.0091; found:
360.0090.
(KBr): 2989, 2919, 1822, 1661, 1271, 1152, 1074, 796 cmÀ1
;
1H NMR (400 MHz, CDCl3): d=7.80 (q, J=8.0 Hz, 1H),
7.60 (dd, J=7.6, 1.6 Hz, 1H), 6.84 (dd, J=8.4, 2.8 Hz, 1H),
1.97 (s, 6H); 13C NMR (100 MHz, CDCl3): d=162.5, 152.7,
151.7, 149.0, 141.6, 121.0, 109.5, 87.6, 70.5, 25.0; MS (EI,
70 eV): m/z (%)=349m+], 304, 178, 135 (100), 108; HRMS-
ESI (m/z): calcd for C11H10FINO3 (M+H)+: 349.9684;
found: 349.9684.
(E)-5-(Iodo(pyridin-2-yl)methylene)-4-isobutyl-4-methyl-
1,3-dioxolan-2-one (3d): pale yellow oil; IR (KBr): 2920,
(E)-5-(Iodo(phenyl)methylene)-4,4-dimethyl-1,3-dioxolan-
2-one (3j): yellow solid; mp: 105À1068C; IR (KBr): 3051,
1815, 1647, 1211, 1065, 757 cmÀ1
;
1H NMR (400 MHz,
1
2922, 1803, 1669, 1269, 1140, 1072, 1027, 758 cmÀ1; H NMR
CDCl3): d=7.40–7.32 (m, 4H), 2.47 (d, J=9.6 Hz, 1H),
1.96–1.87 (m, 5H), 1.08 (d, J=6.0 Hz, 3H), 1.02 (d, J=
6.0 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=149.7, 148.0,
138.5, 129.2, 128.7, 128.3, 89.7, 71.0, 44.89, 25.3, 24.7, 23.6;
MS (EI, 70 eV): m/z (%)=373m+], 273, 245 (100), 217, 90;
HRMS-ESI (m/z): calcd for C14H17INO3 (M+H)+: 374.0248;
found: 374.0250.
(400 MHz, CDCl3): d=7.41–7.24 (m, 5H), 1.94 (s, 6H);
13C NMR (100 MHz, CDCl3): d=149.5, 148.7, 138.3, 129.2,
128.7, 128.2, 87.0, 70.0, 25.2; MS (EI, 70 eV): m/z (%):
330m+], 286, 131(100), 115, 91; HRMS-ESI (m/z): calcd for
C12H11INaO3 (M+Na)+: 352.9645; found: 352.9645.
(E)-4-Ethyl-5-(iodo(phenyl)methylene)-4-methyl-1,3-diox-
olan-2-one (3k): pale yellow solid; mp: 64–658C; IR (KBr):
(E)-5-(Iodo(pyridin-2-yl)methylene)-4-isopentyl-4-isopro-
pyl-1,3-dioxolan-2-one (3e): pale yellow oil; IR (KBr): 2971,
1
2960, 1821, 1651, 1283, 1082, 752 cmÀ1; H NMR (400 MHz,
1825, 1650, 1274, 1057, 747 cmÀ1
;
1H NMR (400 MHz,
CDCl3): d=7.41–7.24 (m, 5H), 2.58–2.49 (m, 1H), 2.05–1.92
(m, 1H), 1.92 (s, 3H), 1.05 (t, J=7.2 Hz, 3H); 13C NMR
(100 MHz, CDCl3): d=149.8, 147.4, 138.5, 129.2, 128.7,
128.3, 90.1, 70.6, 30.2, 24.1, 7.5; MS (EI, 70 eV): m/z (%)=
344m+], 244, 216, 145, 89 (100); HRMS-ESI (m/z): calcd for
C13H13INaO3 (M+Na)+: 366.9802; found: 366.9810.
CDCl3): d=8.68 (d, J=4.4 Hz, 1H), 7.74–7.62 (m, 1H), 7.58
(d, J=7.8 Hz, 1H), 7.19 (m, 1H), 2.51 (d, J=4.0 Hz, 1H),
2.48 (d, J=4.0 Hz, 1H), 2.00–1.82 (m, 4H), 1.04 (d, J=
6.4 Hz, 6H), 0.99 (d, J=6.0 Hz, 6H); 13C NMR (100 MHz,
CDCl3): d=154.3, 149.7, 149.6, 149.2, 136.4, 123.6, 123.3,
93.3, 75.2, 44.9, 24.4, 23.9, 23.6; MS (EI, 70 eV): m/z (%)=
415m+], 315, 272, 245 (100), 188, 146, 130, 90, 78; HRMS-
ESI (m/z): calcd for C17H22INO3Na (M+Na)+: 438.0537;
found: 438.0531.
(E)-4,4-Diethyl-5-(iodo(phenyl)methylene)-1,3-dioxolan-
2-one (3l): yellow solid; mp: 103–1048C; IR (KBr): 2960,
1813, 1650, 1265, 1084, 755 cmÀ1
;
1H NMR (400 MHz,
CDCl3): d=7.40–7.24 (m, 5H), 2.57–2.47 (m, 2H), 2.03–1.92
(m, 2H), 1.06 (t, J=7.6 Hz, 6H); 13C NMR (100 MHz,
CDCl3): d=150.1, 145.9, 138.5, 129.2, 128.7, 128.3, 93.6, 71.3,
29.2, 7.3; MS (EI, 70 eV): m/z (%)=358m+], 286, 244, 216,
(E)-4-(Iodo(pyridin-2-yl)methylene)-1,3-dioxaspiro[4.4]-
nonan-2-one (3 f): yellow solid; mp: 103–1058C; IR (KBr):
1
2955, 1816, 1622, 1283, 1028, 754 cmÀ1; H NMR (400 MHz,
Adv. Synth. Catal. 2015, 357, 2556 – 2565
ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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