Y. Zhang, S. Yu et al.
(2C), 128.9, 128.6 (2C), 105.2, 61.5 (2C), 53.4, 23.1, 13.9 ppm (2C);
HRMS (ESI): m/z calcd for C17H22NO5: 320.1492 [M+H]+; found:
320.1496.
d=7.41–7.32 (m, 3H), 7.27–7.24 (m, 2H), 6.80 (d, J=14.4 Hz, 1H), 5.09
(dd, J=5.1, 9.0 Hz, 1H), 4.84 (dd, J=9.5, 14.6 Hz, 1H), 4.74 (t, J=
8.9 Hz, 1H), 4.20–4.12 (m, 3H), 4.01–3.92 (m, 2H), 3.86 (dd, J=0.4,
9.6 Hz, 1H), 1.24 (t, J=7.1 Hz, 3H), 1.06 ppm (t, J=7.1 Hz, 3H);
13C NMR (100 MHz, CDCl3): d=168.2, 167.7, 155.5, 137.5, 129.3 (2C),
128.8, 127.0, 126.0 (2C), 104.6, 70.7, 61.8, 61.5, 58.3, 53.4, 14.0, 13.8 ppm;
IR (thin film): n˜ =2983, 1765, 1672, 1476, 1458, 1408, 1368, 1299, 1216,
1176, 1127, 1073, 1034, 947, 758, 701 cmÀ1; HRMS (ESI): m/z calcd for
C18H22NO6: 348.1442 [M+H]+; found: 348.1444.
(E)-Diethyl 2-[2-(N-phenylbenzamido)vinyl]malonate (3e): According to
general procedure A, 1e (111 mg, 0.5 mmol), 2a (143 mg, 0.6 mmol),
Na2HPO4 (142 mg, 1 mmol), and [IrACHTNUTRGENN(GU ppy)2HCATUNGTERNN(UGN dtbbpy)PF6] (5 mg,
0.005 mmol) in CH3CN (2.5 mL) afforded 3e (181 mg, 95%) as a color-
less oil. 1H NMR (400 MHz, CDCl3): d=7.62 (d, J=14.4 Hz, 1H), 7.33–
7.28 (m, 4H), 7.26–7.22 (m, 2H), 7.20–7.16 (m, 2H), 7.13–7.11 (m, 2H),
4.97 (dd, J=9.6, 14.4 Hz, 1H), 4.23–4.11 (m, 4H), 4.06 (d, J=9.6 Hz,
1H), 1.25 ppm (t, J=7.1 Hz, 6H); 13C NMR (100 MHz, CDCl3): d=
169.0, 168.3 (2C), 139.4, 135.0, 133.6, 130.1, 129.6 (2C), 129.0 (2C), 128.6
(2C), 128.1, 127.8 (2C), 106.7, 61.7 (2C), 53.5, 14.0 ppm (2C); IR (thin
film): n˜ =3087, 2980, 1735, 1664, 1596, 1494, 1448, 1375, 1326, 1309, 1215,
1180, 1116, 1025, 952, 733, 700, 657, 585, 517 cmÀ1; HRMS (ESI): m/z
calcd for C22H24NO5: 382.1649 [M+H]+; found: 382.1676.
AHCTUNGTRENNUNG
A
CHTUNGTRENNUNG
0.005 mmol) in CH3CN (2.5 mL) afforded 3l (113 mg, 72%) as a color-
less oil. [a]2D0 =À62.5 (c=0.40, in CH3CN); 1H NMR (400 MHz, CDCl3):
d=6.76 (d, J=14.7 Hz, 1H), 5.17 (dd, J=9.6, 14.7 Hz, 1H), 4.32–4.18 (m,
6H), 4.11–4.07 (m, 1H), 4.00 (d, J=9.6 Hz, 1H), 2.49–2.41 (m, 1H),
1.30–1.26 (m, 6H), 0.94 (d, J=7.0 Hz, 3H), 0.84 ppm (d, J=6.9 Hz, 3H);
13C NMR (100 MHz, CDCl3): d=168.4, 168.3, 155.4, 127.2, 102.9, 63.2,
61.9, 61.8, 58.2, 53.4, 26.0, 17.8, 14.0, 13.9 ppm; IR (thin film): n˜ =2966,
2936, 1750, 1672, 1466, 1415, 1394, 1369, 1316, 1217, 1178, 1151, 1123,
1031, 951, 863, 759, 700 cmÀ1; HRMS (ESI): m/z calcd for C15H24NO6:
314.1598 [M+H]+; found: 314.1603.
Tetraethyl 2-(acetamidomethylene)propane-1,1,3,3-tetracarboxylate (3 f):
According to general procedure A, 1 f (43 mg, 0.5 mmol), 2a (600 mg,
1.25 mmol), Na2HPO4 (142 mg, 1 mmol), and [IrACHTUNTRGENN(GU ppy)2AHCTUNGTRENN(GUN dtbbpy)PF6]
(5 mg, 0.005 mmol) in CH3CN (2.5 mL) afforded 3 f (114 mg, 57%) as a
1
white solid powder. H NMR (400 MHz, CDCl3): d=8.85 (d, J=10.3 Hz,
1H), 7.04 (d, J=10.5 Hz, 1H), 4.53 (s, 1H), 4.26–4.12 (m, 8H), 4.07 (s,
1H), 2.06 (s, 3H), 1.30–1.25 ppm (m, 12H); 13C NMR (100 MHz, CDCl3):
d=168.6 (2C), 167.9, 167.8 (2C), 129.3, 105.4, 62.2 (2C), 61.8 (2C), 57.9,
51.7, 23.3, 13.9 ppm (4C); IR (thin film): n˜ =2984, 1732, 1665, 1508, 1446,
1370, 1304, 1220, 1177, 1152, 1096, 1034 cmÀ1; HRMS (ESI): m/z calcd
for C18H28NO9: 402.1759 [M+H]+; found: 402.1766.
Diethyl 2-[1-(Benzyloxycarbonyl)-1,4,5,6-tetrahydropyridin-3-yl]malonate
(3m): According to general procedure A, 1m (110 mg, 0.5 mmol), 2a
(143 mg, 0.6 mmol), Na2HPO4 (142 mg, 1 mmol), and [Ir
ACHTUNGTRENNUNG(ppy)2-
AHCTUNGTRENNUNG
(150 mg, 80%) as a colorless oil. 1H NMR (400 MHz, CDCl3): d=7.36–
7.28 (m, 5H), 6.97 and 6.86 (both s, 1H, rotamers), 5.17 (s, 2H), 4.21–
4.16 (m, 4H), 4.02 and 3.95 (both s, 1H, rotamers), 3.62–3.58 (m, 2H),
2.20 (t, J=5.8 Hz, 2H), 1.87–1.82 (m, 2H), 1.28–1.2 ppm (m, 6H);
13C NMR (100 MHz, CDCl3): d=168.2 (2C), 153.5 and 152.9 (1C, rotam-
ers), 136.2 and 136.1 (1C, rotamers), 128.5 (2C), 128.3 and 128.2 (1C, ro-
tamers), 128.2, 128.0, 126.0 and 125.4 (1C, rotamers), 111.4 and 110.8
(1C, rotamers), 67.7 and 67.5 (1C, rotamers), 61.5, 61.4, 57.3, 42.1 and
41.0 (1C, rotamers), 23.4 and 22.9 (1C, rotamers), 21.4 and 21.2 (1C, ro-
tamers), 14.0 ppm (2C); IR (thin film): n˜ =2981, 1731, 1708, 1668, 1446,
Diethyl 2-(1-benzyl-6-oxo-1,4,5,6-tetrahydropyridin-3-yl)malonate (3g):
According to general procedure A, 1g (93 mg, 0.5 mmol), 2a (143 mg,
0.6 mmol), Na2HPO4 (142 mg, 1 mmol), and [IrACTHNUGRTENNUG(ppy)2ACHTUGNTERN(NUGN dtbbpy)PF6] (5 mg,
0.005 mmol) in CH3CN (2.5 mL) afforded 3g (140 mg, 81%) as a color-
1
less oil. H NMR (400 MHz, CDCl3): d=7.33–7.21 (m, 5H), 6.07 (s, 1H),
4.68 (s, 2H), 4.22–4.15 (m, 4H), 3.98 (s, 1H), 2.62 (t, J=7.6 Hz, 2H), 2.49
(t, J=7.8 Hz, 2H), 1.24 ppm (t, J=7.2 Hz, 6H); 13C NMR (100 MHz,
CDCl3): d=169.1, 167.7 (2C), 136.9, 129.5, 128.7 (2C), 127.6 (2C), 127.6,
112.3, 61.7 (2C), 55.8, 48.9, 31.2, 22.6, 14.0 ppm (2C); IR (thin film): n˜ =
2981, 2936, 1731, 1675, 1443, 1406, 1379, 1304, 1271, 1177, 1146, 1094,
1408, 1311, 1260, 1177, 1147, 1110, 1030, 989, 861, 761, 698, 602 cmÀ1
;
1031, 730, 701, 499 cmÀ1
; HRMS (ESI): m/z calcd for C19H24NO5:
HRMS (ESI): m/z calcd for C20H26NO6: 376.1755 [M+H]+; found:
346.1649 [M+H]+; found: 346.1652.
376.1758.
(E)-Diethyl 2-[1-(2-oxopyrrolidin-1-yl)prop-1-en-2-yl]malonate (3h): Ac-
cording to general procedure A, 1h (62 mg, 0.5 mmol), 2a (143 mg,
0.6 mmol), Na2HPO4 (142 mg, 1 mmol), and [IrACTHNUGRTENNUG(ppy)2ACHTUGNTERN(NUGN dtbbpy)PF6] (5 mg,
Diethyl
nate (3n): According to general procedure A, 1n (91 mg, 0.5 mmol), 2a
(143 mg, 0.6 mmol), Na2HPO4 (142 mg, 1 mmol), and [Ir(ppy)2-
(dtbbpy)PF6] (5 mg, 0.005 mmol) in CH3CN (2.5 mL) afforded 3n
2-[1-(tert-butoxycarbonyl)-1,4,5,6-tetrahydropyridin-3-yl]malo-
ACHTUNGTRENNUNG
0.005 mmol) in CH3CN (2.5 mL) afforded 3h (96 mg, 68%) as a colorless
AHCTUNGTRENNUNG
1
(140 mg, 82%) as a colorless oil. 1H NMR (400 MHz, CDCl3): d=6.94
and 6.78 (both s, 1H, rotamers), 4.23–4.19 (m, 4H), 4.00 and 3.97 (both s,
1H, rotamers), 3.56–3.49 (m, 2H), 2.18 (t, J=5.6 Hz, 2H), 1.88–1.80 (m,
2H), 1.48 (s, 9H), 1.32–1.24 ppm (m, 6H); 13C NMR (100 MHz, CDCl3):
d=168.3 (2C), 152.6 and 151.9 (1C, rotamers), 126.1 and 126.0 (1C, ro-
tamers), 110.0 and 109.3 (1C, rotamers), 80.9 and 80.7 (1C, rotamers),
61.4, 61.3, 57.5 and 57.4 (1C, rotamers), 42.2 and 41.2 (1C, rotamers),
28.2 (3C), 23.4 and 22.9 (1C, rotamers), 21.5 and 21.3 (1C, rotamers),
14.0 ppm (2C); IR (thin film): n˜ =2979, 2936, 1733, 1703, 1665, 1394,
1367, 1306, 1255, 1156, 1033, 989, 855, 767 cmÀ1; HRMS (ESI): m/z calcd
for C17H28NO6: 342.1911 [M+H]+; found: 342.1917.
oil. H NMR (400 MHz, CDCl3): d=6.48 (s, 1H), 4.27–4.15 (m, 4H), 4.05
(s, 1H), 3.81 (t, J=7.0 Hz, 2H), 2.42 (t, J=8.1 Hz, 2H), 2.13–2.05 (m,
2H), 1.92 (d, J=1.0 Hz, 3H), 1.28 ppm (t, J=7.1 Hz, 6H); 13C NMR
(100 MHz, CDCl3): d=174.9, 168.2 (2C), 125.5, 116.8, 61.6 (2C), 59.2,
48.5, 30.3, 18.8, 14.6, 14.0 ppm (2C); IR (thin film): n˜ =2981, 2929, 1731,
1701, 1462, 1408, 1385, 1368, 1302, 1264, 1208, 1149, 1095, 1032 cmÀ1
;
HRMS (ESI): m/z calcd for C14H22NO5: 284.1492 [M+H]+; found:
284.1497.
(E)-Diethyl 2-[2-(2-Oxooxazolidin-3-yl)vinyl]malonate (3j): According
to general procedure A, 1j (56 mg, 0.5 mmol), 2a (143 mg, 0.6 mmol),
Na2HPO4 (142 mg, 1 mmol), and [IrACHTNUTRGENN(GU ppy)2HCATUNGTERNN(UGN dtbbpy)PF6] (5 mg,
0.005 mmol) in CH3CN (2.5 mL) afforded 3j (115 mg, 85%) as a color-
less oil. IR (thin film): n˜ =2984, 1747, 1671, 1481, 1416, 1369, 1330, 1301,
(E)-Ethyl 2,2-difluoro-4-(2-oxopyrrolidin-1-yl)but-3-enoate (3o): Accord-
ing to general procedure A, 1a (56 mg, 0.5 mmol), 2b (121 mg,
0.6 mmol), Na2HPO4 (142 mg, 1 mmol), and [IrACHTUNGRTENNUG(dFCF3ppy)2CAHTUNGTREN(NGUN dtbbpy)PF6]
1229, 1177, 1152, 1129, 1076, 1031, 948, 757 cmÀ1 1H NMR (400 MHz,
;
CDCl3): d=6.86 (d, J=14.3 Hz, 1H), 5.06 (dd, J=9.5, 14.4 Hz, 1H),
4.50–4.46 (m, 2H), 4.26–4.17 (m, 4H), 4.04 (dd, J=0.4, 9.4 Hz, 1H), 3.78
(t, J=8.3 Hz, 2H), 1.28 ppm (t, J=7.1 Hz, 6H); 13C NMR (100 MHz,
CDCl3): d=168.2 (2C), 155.2, 128.3, 102.1, 62.4, 61.8 (2C), 53.0, 42.3,
13.9 ppm (2C); HRMS (ESI): m/z calcd for C12H18NO6: 272.1129
[M+H]+; found: 272.1130.
(5.6 mg, 0.005 mmol) in CH3CN (2.5 mL) afforded 3o (91 mg, 78%) as a
colorless oil. 1H NMR (400 MHz, CDCl3): d=7.56 (dt, J=14.5, 2.2 Hz,
1H), 5.08 (dt, J=14.5, 11.0 Hz, 1H), 4.33 (q, J=7.1 Hz, 2H), 3.54 (t, J=
7.3 Hz, 2H), 2.54 (t, J=8.2 Hz, 2H), 2.21–2.13 (m, 2H), 1.36 ppm (t, J=
7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=173.9, 164.0 (t, J=35.2 Hz;
1C), 130.4 (t, J=10.6 Hz; 1C), 113.0 (t, J=246.9 Hz; 1C), 101.1 (t, J=
26.2 Hz; 1C), 63.0, 44.8, 30.9, 17.4, 13.9 ppm; 19F NMR (376 MHz,
CDCl3): d=À99.8 ppm (2F); IR (thin film): n˜ =3448, 2984, 1764, 1721,
ACHTUNGTRENNUNG
1658, 1462, 1402, 1338, 1303, 1229, 1181, 1076, 1036, 966, 851 cmÀ1
;
A
CHTUNGTRENNUNG
0.005 mmol) in CH3CN (2.5 mL) afforded 3k (144 mg, 83%) as a color-
less oil. [a]2D0 =À83.3 (c=2.77, in CH3CN); 1H NMR (400 MHz, CDCl3):
HRMS (ESI): m/z calcd for C10H14F2NO3: 234.0936 [M+H]+; found:
234.0940.
&
6
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ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 0000, 00, 0 – 0
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