A dry and nitrogen-flushed 10-mL Schlenk flask, equipped with a magnetic stirring bar and a septum, was sequentially charged with a solution of 79 (0.1 mmol), Bu3P (1.2 equiv), acyl chloride 72 (1.1 equiv) and Et3N (1.2 equiv) in CH2Cl2. The reaction mixture was stirred for corresponding time at 30 ℃. Thereafter, the solvent was removed by evaporation in vacuo. Purification by flash chromatography (SiO2, hexanes: EtOAc, 10:1) furnished 83.
103
2-6-3. 實驗數據
(E)-2,2-dibenzyl-1,5-diphenylpent-4-ene-1,3-dione (79b)
Prepared according to General procedure A from precursor 105 (1.25 g, 5 mmol), K2CO3 (2.07 g, 3 equiv), NaI (2.25 g, 3 equiv) and BnBr (1.31 mL, 2.2 equiv) in acetone (25 mL) [reaction condition: 30 ℃ for 24 h]. Purification by flash chromatography (SiO2, hexanes: EtOAc, 10:1) furnished 79b as white solid (0.99 g, 46%).
m.p: 153.8-154.3 ℃; Rf : 0.80 (hexanes: EtOAc, 5:1)
1H-NMR (400 MHz, CDCl3): δ/ppm = 8.00 (d, 2H, J = 8.0 Hz), 7.66 (d, 1H, J = 15.5 Hz), 7.45 (t, 1H, J = 7.3 Hz), 7.38-7.27 (m, 7H), 7.20-7.12 (m, 6H), 7.07-7.00 (m, 4H), 6.49 (d, 1H, J = 15.5 Hz), 3.55 (d, 2H, J = 14.6 Hz), 3.46 (d, 2H, J = 14.6 Hz).
13C-NMR (100 MHz, CHCl3): δ/ppm = 198.8, 197.5, 143.4, 136.9, 136.2, 134.2, 133.0, 130.7, 130.5, 129.2, 128.8, 128.6, 128.1, 126.7, 123.8, 69.5, 39.2
IR (KBr): 𝑣̃ (cm-1) = 1666, 1604, 1449.
HRMS (ESI) for C31H27O2, [M+H]+ (431.2006), found 431.2007.
104
(E)-2,2-dibenzyl-1-(4-methoxyphenyl)-5-phenylpent-4-ene-1,3-dione (79c)
Prepared according to General procedure A from precursor 105 (1.40 g, 5 mmol), K2CO3 (2.07 g, 3 equiv), NaI (2.25 g, 3 equiv) and BnBr (1.31 mL, 2.2 equiv) in acetone (25 mL) [reaction condition: 30 ℃ for 24 h]. Purification by flash chromatography (SiO2, hexanes: EtOAc, 10:1) furnished 79c as white solid (0.90 g, 39%).
m.p: 192.7-193.2 ℃; Rf : 0.64 (hexanes: EtOAc, 5:1)
1H-NMR (400 MHz, CDCl3): δ/ppm = 7.83 (d, 2H, J = 8.8 Hz), 7.64 (d, 1H, J = 15.5 Hz), 7.36-7.27 (m, 5H), 7.20-7.13 (m, 6H), 7.07-7.01 (m, 4H), 6.81 (d, 2H, J = 8.8 Hz), 6.47 (d, 1H, J = 15.5 Hz), 3.80 (s, 3H), 3.52 (d, 2H, J = 14.6 Hz), 3.44 (d, 2H, J
= 15.0 Hz).
13C-NMR (100 MHz, CHCl3): δ/ppm = 198.0, 196.7, 163.3, 143.1, 136.4, 134.3, 131.6, 130.7, 130.6, 129.8, 128.8, 128.6, 128.1, 126.7, 124.0, 113.8, 69.2, 55.4, 39.3.
IR (KBr): 𝑣̃ (cm-1) = 3060, 3028, 1655, 1594, 1450, 1330, 703.
HRMS (ESI) for C32H29O3, [M+H]+ (461.2111), found 461.2113.
105
(E)-2,2-dibenzyl-1-(4-chlorophenyl)-5-phenylpent-4-ene-1,3-dione (79d)
Prepared according to General procedure A from precursor 105 (1.42 g, 5 mmol), K2CO3 (2.07 g, 3 equiv), NaI (2.25 g, 3 equiv) and BnBr (1.31 mL, 2.2 equiv) in acetone (25 mL) [reaction condition: 30 ℃ for 24 h]. Purification by flash chromatography (SiO2, hexanes: EtOAc, 10:1) furnished 79d as white solid (1.35 g, 58%).
m.p: 181.5-182.0 ℃; Rf : 0.83 (hexanes: EtOAc, 5:1)
1H-NMR (400 MHz, CDCl3): δ/ppm = 7.73 (d, 2H, J = 8.7 Hz), 7.67 (d, 1H, J = 15.4 Hz), 7.37-7.27 (m, 7H), 7.21-7.13 (m, 6H), 7.07-7.00 (m, 4H), 6.46 (d, 1H, J = 15.5 Hz), 3.53 (d, 2H, J = 14.8 Hz), 3.44 (d, 2H, J = 14.7 Hz).
13C-NMR (100 MHz, CHCl3): δ/ppm = 197.5, 197.4, 143.8, 139.6, 136.0, 135.2, 134.1, 130.9, 130.6, 130.5, 128.9, 128.8, 128.7, 128.2, 126.9, 123.6, 69.5, 39.3.
IR (KBr): 𝑣̃ (cm-1) = 3060, 3027, 1661, 1598, 755, 700.
HRMS (EI) for C31H2535
ClO2, [M]+ (464.1543), found 464.1544.
HRMS (EI) for C31H2537ClO2, [M]+ (466.1514), found 466.1526.
106
(E)-2,2-dibenzyl-1-(4-nitrophenyl)-5-phenylpent-4-ene-1,3-dione (79e)
Prepared according to General procedure A from precursor 105 (1.48 g, 5 mmol), K2CO3 (2.07 g, 3 equiv), NaI (2.25 g, 3 equiv) and BnBr (1.31 mL, 2.2 equiv) in acetone (25 mL) [reaction condition: 30 ℃ for 24 h]. Purification by flash chromatography (SiO2, hexanes: EtOAc, 10:1) furnished 79e as white solid (0.97 g, 41%).
m.p: 117.9-118.6 ℃; Rf : 0.50 (hexanes: EtOAc, 10:1)
1H-NMR (400 MHz, CDCl3): δ/ppm = 8.13 (d, 2H, J = 8.7 Hz), 7.82 (d, 2H, J = 8.7 Hz), 7.71 (d, 1H, J = 15.4 Hz), 7.43-7.27 (m, 5H), 7.22-7.14 (m, 6H), 7.09-6.99 (m, 4H), 6.48 (d, 1H, J = 15.5 Hz), 3.56 (d, 2H, J = 14.8 Hz), 3.49 (d, 2H, J = 14.8 Hz).
13C-NMR (100 MHz, CHCl3): δ/ppm = 198.0, 196.7, 149.8, 144.5, 141.6, 135.6, 133.8, 131.2, 130.4, 130.0, 129.0, 128.7, 128.3, 127.1, 123.6, 123.0, 69.9, 39.3.
IR (KBr): 𝑣̃ (cm-1) = 3060, 3028, 1668, 1604, 1348, 703.
HRMS (EI) for C31H25NO4, [M]+ (475.1784), found 475.1787.
107
(E)-2,2-dibenzyl-1-(3-chlorophenyl)-5-phenylpent-4-ene-1,3-dione (79f)
Prepared according to General procedure A from precursor 105 (1.42 g, 5 mmol), K2CO3 (2.07 g, 3 equiv), NaI (2.25 g, 3 equiv) and BnBr (1.31 mL, 2.2 equiv) in acetone (25 mL) [reaction condition: 30 ℃ for 24 h]. Purification by flash chromatography (SiO2, hexanes: EtOAc, 10:1) furnished 79f as white solid (1.19 g, 51%).
m.p: 184.2-185.0 ℃; Rf : 0.65 (hexanes: EtOAc, 10:1)
1H-NMR (400 MHz, CDCl3): δ/ppm = 7.73 (d, 2H, J = 8.8 Hz), 7.67 (d, 1H, J =15.5 Hz), 7.38-7.27 (m, 7H), 7.22-7.12 (m, 6H), 7.09-6.98 (m, 4H), 6.46 (d, 1H, J = 15.4 Hz), 3.53 (d, 2H, J = 14.7 Hz), 3.45 (d, 2H, J = 14.8 Hz)
13C-NMR (100 MHz, CHCl3): δ/ppm = 197.5, 197.3, 143.8, 139.5, 135.1, 134.0, 130.9, 130.6, 130.5, 129.0, 128.8, 128.6, 128.2, 126.9, 123.5, 69.5, 39.2.
IR (KBr): 𝑣̃ (cm-1) = 3028, 1653, 1578, 1330, 698, 684, 540.
HRMS (EI) for C31H2535
ClO2, [M]+ (464.1543), found 464.1543.
HRMS (EI) for C31H2537ClO2, [M]+ (466.1514), found 466.1510.
108
(E)-2,2-dibenzyl-1-(2-chlorophenyl)-5-phenylpent-4-ene-1,3-dione (79g)
Prepared according to General procedure A from precursor 105 (1.42 g, 5 mmol), K2CO3 (2.07 g, 3 equiv), NaI (2.25 g, 3 equiv) and BnBr (1.31 mL, 2.2 equiv) in acetone (25 mL) [reaction condition: 30 ℃ for 24 h]. Purification by flash chromatography (SiO2, hexanes: EtOAc, 10:1) furnished 79g as white solid (0.77 g, 33%).
m.p: 108.7-109.5 ℃; Rf : 0.55 (hexanes: EtOAc, 10:1)
1H-NMR (400 MHz, CDCl3): δ/ppm = 7.57 (d, 2H, J = 15.5 Hz), 7.40-7.34 (m, 2H), 7.33-7.28 (m, 3H), 7.22-7.16 (m, 6H), 7.15-7.06 (m, 5H), 6.92 (d, 1H, J = 7.8 Hz), 6.88 (d, 1H, J = 8.1 Hz), 6.46 (d, 1H, J = 7.8 Hz), 3.50 (s, 4H)
13C-NMR (100 MHz, CHCl3): δ/ppm = 201.2, 195.9, 143.0, 138.4, 136.0, 134.1, 131.6, 131.4, 130.6, 128.8, 128.4, 128.2, 127.0, 126.8, 126.1, 123.1, 71.4, 40.1
IR (KBr): 𝑣̃ (cm-1) = 3060, 3027, 1672, 1604, 1329, 720, 701, 544.
HRMS (EI) for C31H2535
ClO2, [M]+ (464.1543), found 464.1542.
HRMS (EI) for C31H2537ClO2, [M]+ (466.1514), found 466.1519.
109
(E)-2,2-dibenzyl-5-(4-bromophenyl)-1-phenylpent-4-ene-1,3-dione (79a)
Prepared according to General procedure A from precursor 105 (1.65 g, 5 mmol), K2CO3 (2.07 g, 3 equiv), NaI (2.25 g, 3 equiv) and BnBr (1.31 mL, 2.2 equiv) in acetone (25 mL) [reaction condition: 30 ℃ for 24 h]. Purification by flash chromatography (SiO2, hexanes: EtOAc, 10:1) furnished 79a as white solid (1.58 g, 62%).
m.p: 189.8-190.6 ℃; Rf : 0.35 (hexanes: EtOAc, 10:1)
1H-NMR (400 MHz, CDCl3): δ/ppm = 7.78 (d, 2H, J = 7.9 Hz), 7.54 (d, 1H, J = 15.4 Hz), 7.45 (t, 1H, J = 7.0 Hz), 7.39 (d, 2H, J = 7.8 Hz), 7.34 (t, 2H, J = 7.6 Hz), 7.20-7.13 (m, 6H), 7.11 (d, 2H, J = 8.1 Hz), 7.03 (d, 4H, J = 6.2 Hz), 6.35 (d, 1H, J = 15.4 Hz), 3.56 (d, 2H, J = 14.5 Hz), 3.44 (d, 2H, J = 14.5 Hz).
13C-NMR (100 MHz, CHCl3): δ/ppm = 198.6, 197.5, 141.7, 136.9, 136.2, 133.1, 132.0, 130.6, 129.9, 129.2, 128.7, 128.1, 126.8, 125.1, 124.5, 69.6, 39.5.
IR (KBr): 𝑣̃ (cm-1) = 1622, 1611, 529.
HRMS (ESI) for C31H2679
BrO2, [M+H]+ (509.1116), found 509.1113.
HRMS (ESI) for C31H2681BrO2, [M+H]+ (511.1096), found 511.1073.
110
(E)-2,2-dibenzyl-5-(3-bromophenyl)-1-phenylpent-4-ene-1,3-dione (79h)
Prepared according to General procedure A from precursor 105 (1.65 g, 5 mmol), K2CO3 (2.07 g, 3 equiv), NaI (2.25 g, 3 equiv) and BnBr (1.31 mL, 2.2 equiv) in acetone (25 mL) [reaction condition: 30 ℃ for 24 h]. Purification by flash chromatography (SiO2, hexanes: EtOAc, 10:1) furnished 79h as white solid (1.45 g, 57%).
m.p: 121.0-121.7 ℃; Rf : 0.63 (hexanes: EtOAc, 10:1)
1H-NMR (400 MHz, CDCl3): δ/ppm = 7.78 (d, 2H, J = 7.4 Hz), 7.52 (d, 1H, J = 15.5 Hz), 7.49-7.40 (m, 2H), 7.39-7.31 (m, 3H), 7.23-7.10 (m, 8H), 7.09-6.99 (m, 4H), 6.33 (d, 1H, J = 15.5 Hz), 3.56 (d, 2H, J = 14.6 Hz), 3.44 (d, 2H, J = 14.8 Hz)
13C-NMR (100 MHz, CHCl3): δ/ppm = 198.5, 197.4, 141.3, 136.8, 136.3, 136.0, 133.4, 133.1, 131.0, 130.6, 130.2, 129.2, 128.7, 128.1, 127.1, 126.8, 125.1, 122.9, 69.5, 39.5.
IR (KBr): 𝑣̃ (cm-1) = 3060, 3030, 1666, 1604, 1128, 976, 726, 700, 611.
HRMS (EI) for C31H2579
BrO2, [M]+ (508.1038), found 508.1040.
HRMS (EI) for C31H2581BrO2, [M]+ (510.1017), found 510.1047.
111
(E)-2,2-dibenzyl-5-(2-bromophenyl)-1-phenylpent-4-ene-1,3-dione (79i)
Prepared according to General procedure A from precursor 105 (1.65 g, 5 mmol), K2CO3 (2.07 g, 3 equiv), NaI (2.25 g, 3 equiv) and BnBr (1.31 mL, 2.2 equiv) in acetone (25 mL) [reaction condition: 30 ℃ for 24 h]. Purification by flash chromatography (SiO2, hexanes: EtOAc, 10:1) furnished 79i as white solid (1.20 g, 47%).
m.p: 151.5-152.5 ℃; Rf : 0.40 (hexanes: EtOAc, 10:1)
1H-NMR (400 MHz, CDCl3): δ/ppm = 7.94 (d, 1H, J = 1.54 Hz), 7.79 (d, 2H, J = 7.5 Hz), 7.55-7.49 (m, 1H), 7.47 (t, 1H, J = 7.5 Hz), 7.36 (t, 2H, J = 7.7 Hz), 7.22-7.14 (m, 6H), 7.14-7.10 (m, 2H), 7.09-7.03 (m, 4H), 7.01-6.94 (m, 1H), 6.24 (d, 1H, J = 15.4 Hz), 3.57 (d, 2H, J = 14.5 Hz), 3.43 (d, 2H, J = 14.5 Hz)
13C-NMR (100 MHz, CHCl3): δ/ppm = 198.5, 197.3, 141.3, 136.7, 136.1, 134.4, 133.3, 133.1, 131.4, 130.6, 129.2, 128.6, 128.1, 127.9, 127.4, 126.9, 126.8, 125.9, 69.5, 39.7.
IR (KBr): 𝑣̃ (cm-1) = 3057, 3028, 1693, 1662, 1605, 1446, 980, 751, 701, 533.
HRMS (EI) for C31H2579
BrO2, [M]+ (508.1038), found 508.1036.
HRMS (EI) for C31H2581BrO2, [M]+ (510.1017), found 510.1045.
112
(E)-2,2-dibenzyl-5-(4-methoxyphenyl)-1-phenylpent-4-ene-1,3-dione (79j)
Prepared according to General procedure A from precursor 105 (1.40 g, 5 mmol), K2CO3 (2.07 g, 3 equiv), NaI (2.25 g, 3 equiv) and BnBr (1.31 mL, 2.2 equiv) in acetone (25 mL) [reaction condition: 30 ℃ for 24 h]. Purification by flash chromatography (SiO2, hexanes: EtOAc, 10:1) furnished 79j as white solid (1.20 g, 52%).
m.p: 114.3-115.0 ℃; Rf : 0.53 (hexanes: EtOAc, 10:1)
1H-NMR (400 MHz, CDCl3): δ/ppm = 7.81 (d, 2H, J = 7.8 Hz), 7.65 (d, 1H, J = 15.4 Hz), 7.45 (t, 1H, J = 7.3 Hz), 7.34 (t, 2H, J = 7.7 Hz), 7.29 (d, 2H, J = 8.29 Hz), 7.22-7.10 (m, 6H), 7.08-6.98 (m, 4H), 6.80 (d, 2H, J = 8.7 Hz), 6.41 (d, 1H, J = 15.4 Hz), 3.79 (s, 3H), 3.54 (d, 2H, J = 14.8 Hz), 3.46 (d, 2H, J = 14.8 Hz)
13C-NMR (100 MHz, CHCl3): δ/ppm = 199.0, 197.3, 161.8, 143.3, 136.9, 136.3, 132.9, 130.5, 130.4, 129.2, 128.5, 128.0, 126.9, 126.6, 121.5, 114.2, 69.4, 55.3, 39.0
IR (KBr): 𝑣̃ (cm-1) = 3059, 3024, 1686, 1661, 1449, 985, 763, 702.
HRMS (EI) for C32H28O3, [M]+ (460.2038), found 460.2043.
113
(E)-2,2-dibenzyl-5-(furan-2-yl)-1-phenylpent-4-ene-1,3-dione (79k)
Prepared according to General procedure A from precursor 105 (1.20 g, 5 mmol), K2CO3 (2.07 g, 3 equiv), NaI (2.25 g, 3 equiv) and BnBr (1.31 mL, 2.2 equiv) in acetone (25 mL) [reaction condition: 30 ℃ for 24 h]. Purification by flash chromatography (SiO2, hexanes: EtOAc, 10:1) furnished 79k as white solid (0.9 g, 43%).
m.p: 180.7-181.3 ℃; Rf : 0.66 (hexanes: EtOAc, 5:1)
1H-NMR (400 MHz, CDCl3): δ/ppm = 7.83 (d, 2H, J = 8.4 Hz), 7.52-7.46 (m, 2H), 7.42 (s, 1H), 7.38 (t, 2H, J = 7.7 Hz), 7.23-7.17 (m, 6H), 7.06-7.01 (m, 4H), 6.65 (d, 1H, J = 3.5 Hz), 6.59 (d, 1H, J = 15.4 Hz), 6.45 (dd, 1H, J = 3.3 Hz, J = 1.8 Hz), 3.53 (s, 4H)
13C-NMR (100 MHz, CHCl3): δ/ppm = 198.8, 197.3, 151.1, 145.2, 137.1, 136.3, 132.9, 130.5, 129.6, 129.2, 128.6, 128.1, 126.7, 121.0, 116.9, 112.6, 69.4. 38.6.
IR (KBr): 𝑣̃ (cm-1) = 3059, 3029, 1658, 1593, 1318, 1071, 751, 698.
HRMS (EI) for C29H24O3, [M]+ (420.1725), found 420.1731.
114
(Z)-2,2-dibenzyl-1,5,6-triphenylhex-4-ene-1,3,6-trione (83ba)
Prepared according to TP 1 from 79b (43.1 mg, 0.1 mmol), Bu3P (33.0 μL, 1.2 equiv), benzoyl chloride 72a (13.0 μL, 1.1 equiv), Et3N (17.0 μL, 1.2 equiv) in CH2Cl2. [reaction condition: 30 ℃ for 2 h]. Purification by flash chromatography (SiO2, hexanes: EtOAc, 10:1) furnished 83ba as white solid (37.4 mg, 70%).
m.p: 92.5-93.5 ℃; Rf : 0.61 (hexanes: EtOAc, 5:1)
1H-NMR (400 MHz, CDCl3): δ/ppm = 7.81 (d, 2H, J = 7.9 Hz), 7.80 (d, 2H, J = 7.9 Hz), 7.59 (t, 1H, J = 7.3 Hz), 7.53 (t, 1H, J = 7.3 Hz), 7.47 (t, 2H, J = 7.9 Hz), 7.43 (t, 2H, J = 7.7 Hz), 7.27 (t, 1H, J = 7.7 Hz), 7.23-7.14 (m, 8H), 7.04 (brs, 4H), 6.96 (d, 2H, J = 7.5 Hz), 6.05 (s, 1H), 3.54 (d, 2H, J = 14.6 Hz), 3.26 (brs, 2H)
13C-NMR (100 MHz, CHCl3): δ/ppm = 197.7, 196.8, 154.4, 136.4, 135.8, 133.8, 133.4, 133.3, 130.7, 129.4, 128.9, 128.8, 128.7, 128.6, 128.2, 127.2, 126.9, 123.4, 69.0, 40.4
IR (KBr): 𝑣̃ (cm-1) = 3060, 1667, 182, 699.
HRMS (ESI) for C38H31O3, [M+H]+ (535.2273), found 535.2269.
115
(Z)-2,2-dibenzyl-1-(4-methoxyphenyl)-5,6-diphenylhex-4-ene-1,3,6-trione (83ca)
Prepared according to TP 1 from 79c (46.1 mg, 0.1 mmol), Bu3P (33.0 μL, 1.2 equiv), benzoyl chloride 72a (13.0 μL, 1.1 equiv), Et3N (17.0 μL, 1.2 equiv) in CH2Cl2. [reaction condition: 30 ℃ for 2.5 h]. Purification by flash chromatography (SiO2, hexanes: EtOAc, 10:1) furnished 83ca as white solid (22.0 mg, 39%).
m.p: 254.2-254.7 ℃; Rf : 0.50 (hexanes: EtOAc, 5:1)
1H-NMR (400 MHz, CDCl3): δ/ppm = 7.82 (d, 2H, J = 8.4 Hz), 7.81 (d, 2H, J = 7.9 Hz), 7.59 (t, 1H, J = 7.3 Hz), 7.46 (t, 2H, J = 7.5 Hz), 7.27 (t, 1H, J = 7.3 Hz), 7.23-7.14 (m, 8H), 7.04 (brs, 4H), 6.97 (d, 2H, J = 7.9 Hz), 6.90 (d, 2H, J = 8.4 Hz), 6.06 (s, 1H), 3.85 (s, 3H), 3.53 (d, 2H, J = 14.2 Hz), 3.24 (brs, 2H)
13C-NMR (100 MHz, CHCl3): δ/ppm = 197.4, 197.0, 195.7, 163.5, 154.2, 135.9, 133.9, 133.4, 131.9, 130.8, 130.7, 128.9, 128.8, 128.7, 128.1, 127.2, 126.8, 123.6, 114.0, 68.7, 55.5, 40.5.
IR (KBr): 𝑣̃ (cm-1) = 3028, 1659, 1597, 1171.
HRMS (ESI) for C39H32O4Na, [M+Na]+ (587.2198), found 587.2202.
116
(Z)-2,2-dibenzyl-1-(4-chlorophenyl)-5,6-diphenylhex-4-ene-1,3,6-trione (83da)
Prepared according to TP 1 from 79d (46.5 mg, 0.1 mmol), Bu3P (33.0 μL, 1.2 equiv), benzoyl chloride 72a (13.0 μL, 1.1 equiv), Et3N (17.0 μL, 1.2 equiv) in CH2Cl2. [reaction condition: 30 ℃ for 1 h]. Purification by flash chromatography (SiO2, hexanes: EtOAc, 10:1) furnished 83da as white solid (44.4 mg, 78%).
m.p: 189.4-190.2 ℃; Rf : 0.70 (hexanes: EtOAc, 5:1)
1H-NMR (400 MHz, CDCl3): δ/ppm = 7.80 (d, 2H, J = 7.1 Hz), 7.74 (d, 2H, J = 8.8 Hz), 7.60 (t, 1H, J = 7.3 Hz), 7.47 (t, 2H, J = 7.7 Hz), 7.39 (d, 2H, J = 8.8 Hz), 7.29 (t, 1H, J = 7.3 Hz), 7.23-7.17 (m, 8H), 7.03 (brs, 4H), 6.98 (d, 2H, J = 7.5 Hz), 6.02 (s, 1H), 3.54 (d, 2H, J = 14.6 Hz), 3.24 (brs, 2H).
13C-NMR (100 MHz, CHCl3): δ/ppm = 196.8, 196.4, 154.9, 139.9, 135.8, 134.6, 133.7, 133.5, 130.9, 130.7, 129.1, 129.0, 128.8, 128.7, 128.3, 127.2, 127.0, 123.1, 69.0.
IR (KBr): 𝑣̃ (cm-1) = 3029, 1667, 1585, 699.
HRMS (ESI) for C38H3035ClO3, [M+H]+ (569.1883), found 569.1878.
HRMS (ESI) for C38H3037
ClO3, [M+H]+ (571.1854), found 571.1846.
117
(Z)-2,2-dibenzyl-1-(4-nitrophenyl)-5,6-diphenylhex-4-ene-1,3,6-trione (83ea)
Prepared according to TP 1 from 79e (47.6 mg, 0.1 mmol), Bu3P (33.0 μL, 1.2 equiv), benzoyl chloride 72a (13.0 μL, 1.1 equiv), Et3N (17.0 μL, 1.2 equiv) in CH2Cl2. [reaction condition: 30 ℃ for 3 h]. Purification by flash chromatography (SiO2, hexanes: EtOAc, 10:1) furnished 83ea as white solid (30.1 mg, 52%).
m.p: 150.0-150.2 ℃; Rf : 0.45 (hexanes: EtOAc, 10:1)
1H-NMR (400 MHz, CDCl3): δ/ppm = 8.20 (d, 2H, J = 8.8 Hz), 7.87 (d, 2H, J = 8.8 Hz), 7.80 (d, 2H, J = 7.5 Hz), 7.59 (t, 1H, J = 7.3 Hz), 7.50 (t, 2H, J = 7.7 Hz), 7.28 (t, 1H, J = 7.3 Hz), 7.24-7.15 (m, 8H), 7.03 (brs, 4H), 7.00 (d, 2H, J = 7.5 Hz), 6.06 (s, 1H), 3.58 (d, 2H, J = 14.2 Hz), 3.30 (brs, 2H)
13C-NMR (100 MHz, CHCl3): δ/ppm = 196.8, 196.7, 196.3, 155.8, 150.0, 140.9, 135.7, 135.6, 133.7, 133.5, 131.2, 130.7, 130.5, 129.1, 128.9, 128.8, 128.5, 127.3, 127.2, 123.9, 122.7, 69.4, 40.3
IR (KBr): 𝑣̃ (cm-1) = 3061, 1673, 1582, 1568, 1526, 1347, 1218, 701.
HRMS (ESI) for C38H30NO5, [M+H]+ (580.2124), found 580.2129.
118
(Z)-2,2-dibenzyl-1-(3-chlorophenyl)-5,6-diphenylhex-4-ene-1,3,6-trione (83fa)
Prepared according to TP 1 from 79f (46.5 mg, 0.1 mmol), Bu3P (33.0 μL, 1.2 equiv), benzoyl chloride 72a (13.0 μL, 1.1 equiv), Et3N (17.0 μL, 1.2 equiv) in CH2Cl2. [reaction condition: 30 ℃ for 2 h]. Purification by flash chromatography (SiO2, hexanes: EtOAc, 10:1) furnished 83fa as white solid (42.1 mg, 74%).
m.p: 202.8-203.3 ℃; Rf : 0.58 (hexanes: EtOAc, 10:1)
1H-NMR (400 MHz, CDCl3): δ/ppm = 7.80 (d, 2H, J = 7.9 Hz), 7.7 (d, 2H, J = 8.4 Hz), 7.58 (t, 1H, J = 7.3 Hz), 7.46 (t, 2H, J = 7.5 Hz), 7.38 (d, 2H, J = 8.8 Hz), 7.27 (t, 1H, J = 7.3 Hz), 7.23-7.14 (m, 8H), 7.03 (brs, 4H), 6.98 (d, 2H, J = 7.9 Hz), 6.03 (s, 1H), 3.55 (d, 2H, J = 14.2 Hz), 3.24 (brs, 2H)
13C-NMR (100 MHz, CHCl3): δ/ppm = 196.7, 196.3, 154.8, 139.8, 135.7, 134.5, 133.6, 133.4, 130.8, 130.8, 130.6, 129.1, 128.9, 128.7, 128.6, 128.2, 127.1, 126.9, 123.0, 68.9, 40.3
IR (KBr): 𝑣̃ (cm-1) = 3062, 1668, 1585, 1570, 1218, 733, 699.
HRMS (ESI) for C38H3035ClO3, [M+H]+ (569.1883), found 569.1885.
HRMS (ESI) for C38H3037
ClO3, [M+H]+ (571.1854), found 571.1875.
119
(Z)-2,2-dibenzyl-1-(2-chlorophenyl)-5,6-diphenylhex-4-ene-1,3,6-trione (83ga)
Prepared according to TP 1 from 79g (46.5 mg, 0.1 mmol), Bu3P (33.0 μL, 1.2 equiv), benzoyl chloride 72a (13.0 μL, 1.1 equiv), Et3N (17.0 μL, 1.2 equiv) in CH2Cl2. [reaction condition: 30 ℃ for 43 h]. Purification by flash chromatography (SiO2, hexanes: EtOAc, 10:1) furnished 83ga as white solid (15.3 mg, 27%).
m.p: 82.3-82.9 ℃; Rf : 0.44 (hexanes: EtOAc, 10:1)
1H-NMR (400 MHz, CDCl3): δ/ppm = 7.73 (d, 2H, J = 7.9 Hz), 7.55 (t, 1H, J = 7.3 Hz), 7.41 (d, 1H, J = 7.5 Hz), 7.40 (d, 2H, J = 7.9 Hz), 7.34 (t, 1H, J = 7.3 Hz), 7.27 (t, 3H, J = 7.1 Hz), 7.22-7.14 (m, 8H), 7.11-7.00 (m, 5H), 6.65 (s, 1H), 6.58 (d, 1H, J = 7.5 Hz), 3.48 (d, 2H, J = 14.6 Hz), 3.36 (d, 2H, J = 14.6 Hz)
13C-NMR (100 MHz, CHCl3): δ/ppm = 200.4, 196.9, 195.1, 154.7, 138.1, 135.7, 133.7, 133.3, 132.2, 131.8, 131.3, 130.7, 129.0, 128.6, 128.6, 128.3, 127.5, 127.1, 126.9, 126.5, 122.2, 71.0, 40.5
IR (KBr): 𝑣̃ (cm-1) = 2924, 1673, 1584, 1448, 1217, 699.
HRMS (ESI) for C38H3035ClO3, [M+H]+ (569.1883), found 569.1884.
HRMS (ESI) for C38H3037
ClO3, [M+H]+ (571.1854), found 571.1874.
120
(Z)-2,2-dibenzyl-5-(4-bromophenyl)-1,6-diphenylhex-4-ene-1,3,6-trione (83aa)
Prepared according to TP 1 from 79a (50.9 mg, 0.1 mmol), Bu3P (33.0 μL, 1.2 equiv), benzoyl chloride 72a (13.0 μL, 1.1 equiv), Et3N (17.0 μL, 1.2 equiv) in CH2Cl2. [reaction condition: 30 ℃ for 1 h]. Purification by flash chromatography (SiO2, hexanes: EtOAc, 10:1) furnished 83aa as white solid (52.1 mg, 85%).
m.p: 170.3-170.7 ℃; Rf : 0.70 (hexanes: EtOAc, 5:1)
1H-NMR (400 MHz, CDCl3): δ/ppm = 7.79 (d, 2H, J = 5.3 Hz), 7.77 (d, 2H, J = 4.9 Hz), 7.60 (t, 1H, J = 7.3 Hz), 7.53 (t, 1H, J = 7.3 Hz), 7.47 (t, 2H, J = 7.7 Hz), 7.43 (t, 2H, J = 7.7 Hz), 7.29 (d, 2H, J = 8.8 Hz), 7.23-7.16 (m, 6H), 7.04 (brs, 4H), 6.75 (d, 2H, J = 8.4 Hz), 5.90 (s, 1H), 3.55 (d, 2H, J = 14.1 Hz), 3.23 (brs, 2H).
13C-NMR (100 MHz, CHCl3): δ/ppm = 197.5, 196.9, 196.4, 152.8, 136.4, 135.6, 133.6, 133., 132.7, 132.2, 130.8,129.4, 128.9, 128.7, 128.6, 128.2, 127.0, 125.4, 124.0, 69.1, 40.7.
IR (KBr): 𝑣̃ (cm-1) = 1667, 1579, 529.
HRMS (ESI) for C38H3079BrO3, [M+H]+ (613.1378), found 613.1379.
HRMS (ESI) for C38H3081
BrO3, [M+H]+ (615.1358), found 615.1356.
121
(Z)-2,2-dibenzyl-5-(3-bromophenyl)-1,6-diphenylhex-4-ene-1,3,6-trione (83ha)
Prepared according to TP 1 from 79h (50.9 mg, 0.1 mmol), Bu3P (33.0 μL, 1.2 equiv), benzoyl chloride 72a (13.0 μL, 1.1 equiv), Et3N (17.0 μL, 1.2 equiv) in CH2Cl2. [reaction condition: 30 ℃ for 0.5 h]. Purification by flash chromatography (SiO2, hexanes: EtOAc, 10:1) furnished 83ha as white solid (41.7 mg, 68%).
m.p: 168.8-169.3 ℃; Rf : 0.56 (hexanes: EtOAc, 10:1)
1H-NMR (400 MHz, CDCl3): δ/ppm = 7.79 (t, 4H, J = 6.6 Hz), 7.60 (t, 1H, J = 7.3 Hz), 7.54 (t, 1H, J = 7.3 Hz), 7.49 (d, 2H, J = 7.5 Hz), 7.44 (t, 2H, J = 7.9 Hz), 7.35 (d, 1H, J = 7.9 Hz), 7.30-7.16 (m, 6H), 7.05 (brs, 3H), 7.00 (t, 2H, J = 7.9 Hz), 6.91 (s, 1H), 6.83 (d, 1H, J = 7.5 Hz), 5.79 (s, 1H), 3.57 (d, 2H, J = 14.2 Hz), 3.16 (brs, 2H)
13C-NMR (100 MHz, CHCl3): δ/ppm = 197.2, 196.9, 196.1, 152.4, 136.2, 135.8, 135.4, 133.6, 133.4, 133.4, 130.8, 130.2, 129.6, 129.4, 128.8, 128.8, 128.7, 128.2, 127.1, 125.7, 125.0, 123.0, 69.0, 40.9
IR (KBr): 𝑣̃ (cm-1) = 3061, 2930, 1667, 1585, 1217, 698.
HRMS (ESI) for C38H3079BrO3, [M+H]+ (613.1378), found 613.1382.
HRMS (ESI) for C38H3081
BrO3, [M+H]+ (615.1358), found 615.1367.
122
(Z)-2,2-dibenzyl-5-(furan-2-yl)-1,6-diphenylhex-4-ene-1,3,6-trione (83ka)
Prepared according to TP 1 from 79k (42.1 mg, 0.1 mmol), Bu3P (33.0 μL, 1.2 equiv), benzoyl chloride 72a (13.0 μL, 1.1 equiv), Et3N (17.0 μL, 1.2 equiv) in CH2Cl2. [reaction condition: 30 ℃ for 1 h]. Purification by flash chromatography (SiO2, hexanes: EtOAc, 10:1) furnished 83ka as white solid (40.9 mg, 78%).
m.p: 79.1-79.4 ℃; Rf : 0.50 (hexanes: EtOAc, 5:1)
1H-NMR (400 MHz, CDCl3): δ/ppm = 7.82 (d, 2H, J = 7.2 Hz), 7.77 (d, 2H, J = 7.3 Hz), 7.61 (t, 1H, J = 7.4 Hz), 7.52 (t, 1H, J = 7.3 Hz), 7.47 (t, 2H, J = 7.7 Hz), 7.39 (t, 3H, J = 7.5 Hz), 7.22-7.08 (m, 6H), 7.01-6.93 (m, 4H), 6.48 (s, 1H), 6.36-6.33 (m, 1H), 6.30 (d, 1H, J = 3.5 Hz), 3.60-3.18 (m, 4H)
13C-NMR (100 MHz, CHCl3): δ/ppm = 198.0, 196.5, 194.5, 149.3, 145.7, 143.4, 136.8, 135.6, 133.5, 133.1, 130.5, 129.3, 128.7, 128.7, 128.1, 126.7, 117.7, 116.9, 112.9, 69.1, 39.2
IR (KBr): 𝑣̃ (cm-1) = 3028, 1661, 1573, 699.
HRMS (ESI) for C36H29O4, [M+H]+ (525.2066), found 525.2061.
123
(Z)-2,2-dibenzyl-5-(4-bromophenyl)-6-(4-chlorophenyl)-1-phenylhex-4-ene-1,3,6-t rione (83ab)
Prepared according to TP 1 from 79a (50.9 mg, 0.1 mmol), Bu3P (33.0 μL, 1.2 equiv), 4-chlorobenzoyl chloride 72b (14.4 μL, 1.1 equiv), Et3N (17.0 μL, 1.2 equiv) in CH2Cl2. [reaction condition: 30 ℃ for 0.5 h]. Purification by flash chromatography (SiO2, hexanes: EtOAc, 10:1) furnished 83ab as white solid (51.8 mg, 80%).
m.p: 160-160.7 ℃; Rf : 0.78 (hexanes: EtOAc, 5:1)
1H-NMR (400 MHz, CDCl3): δ/ppm = 7.77 (d, 2H, J = 7.6 Hz), 7.68 (d, 2H, J = 8.5 Hz), 7.54 (t, 1H, J = 7.4 Hz), 7.43 (t, 4H, J = 8.2 Hz), 7.30 (d, 2H, J = 8.5 Hz), 7.23-7.16 (m, 6H), 7.04 (brs, 4H), 6.72 (d, 2H, J = 8.5 Hz), 5.88 (s, 1H), 3.56 (d, 2H, J
= 14.2 Hz), 3.28 (brs, 2H)
13C-NMR (100 MHz, CHCl3): δ/ppm = 197.3, 197.1, 195.2, 152.1, 140.0, 136.3, 134.0, 133.4, 132.3, 132.2, 130.7, 129.9, 129.3, 129.2, 128.8, 128.4, 128.2, 127.0, 125.6, 124.1, 69.0, 40.8
IR (KBr): 𝑣̃ (cm-1) = 1666, 1578, 700, 508.
HRMS (ESI) for C38H2979Br35ClO3, [M+H]+ (647.0989), found 647.0980; [M+2]+ (649.0968), found 649.0964; [M+4]+ (651.0939), found 651.0945.
124
(Z)-2,2-dibenzyl-5-(4-bromophenyl)-6-(4-methoxyphenyl)-1-phenylhex-4-ene-1,3, 6-trione (83ac)
Prepared according to TP 1 from 79a (50.9 mg, 0.1 mmol), Bu3P (33.0 μL, 1.2 equiv), p-toluoyl chloride 72c (14.8 μL, 1.1 equiv), Et3N (17.0 μL, 1.2 equiv) in CH2Cl2. [reaction condition: 30 ℃ for 1 h]. Purification by flash chromatography (SiO2, hexanes: EtOAc, 10:1) furnished 83ac as white solid (34.7 mg, 54%).
m.p: 102.3-102.8 ℃; Rf : 0.35 (hexanes: EtOAc, 10:1)
1H-NMR (400 MHz, CDCl3): δ/ppm = 7.80 (d, 2H, J = 8.1 Hz), 7.74 (d, 2H, J = 7.6 Hz), 7.53 (t, 1H, J = 7.3 Hz), 7.44 (t, 2H, J = 7.6 Hz), 7.28 (d, 2H, J = 8.6 Hz), 7.20 (brs, 6H), 7.11 (brs, 3H), 6.95 (d, 3H, J = 8.8 Hz), 6.75 (d, 2H, J = 8.6 Hz), 5.86 (s, 1H), 3.89 (s, 3H), 3.56 (d, 2H, J = 14.2 Hz), 3.35 (brs, 1H), 3.10 (brs, 1H)
13C-NMR (100 MHz, CHCl3): δ/ppm = 197.5, 196.8, 195.0, 163.9, 152.8, 136.3, 133.4, 132.9. 132.1, 131.0, 130.8, 129.4, 128.8, 128.5, 128.2, 126.9, 125.2, 123.6, 114.1, 69.1, 55.5, 40.6
IR (KBr): 𝑣̃ (cm-1) = 2921, 1665, 1597, 1579, 1259, 1164, 699.
HRMS (ESI) for C39H3279BrO4, [M+H]+ (643.1484), found 643.1482.
HRMS (ESI) for C39H3281
BrO4, [M+H]+ (645.1464), found 645.1469.
125
(Z)-2,2-dibenzyl-5-(4-bromophenyl)-6-(4-nitrophenyl)-1-phenylhex-4-ene-1,3,6-tr ione (83ad)
Prepared according to TP 1 from 79a (50.9 mg, 0.1 mmol), Bu3P (33.0 μL, 1.2 equiv), 4-nitrobenzoyl chloride 72d (20.8 mg, 1.1 equiv), Et3N (17.0 μL, 1.2 equiv) in CH2Cl2. [reaction condition: 30 ℃ for 0.5 h]. Purification by flash chromatography (SiO2, hexanes: EtOAc, 10:1) furnished 83ad as white solid (14.5 mg, 22%).
m.p: 219.2-219.5 ℃; Rf : 0.53 (hexanes: EtOAc, 10:1)
1H-NMR (400 MHz, CDCl3): δ/ppm = 8.31 (d, 2H, J = 8.6 Hz), 7.88 (d, 2H, J = 8.4 Hz), 7.75 (d, 2H, J = 7.6 Hz), 7.56 (t, 1H, J = 7.3 Hz), 7.44 (t, 2H, J = 7.7 Hz), 7.33 (d, 2H, J = 8.5 Hz), 7.25-7.16 (m, 6H), 7.04 (brs, 4H), 6.72 (d, 2H, J = 8.5 Hz), 5.91 (s, 1H), 3.56 (d, 2H, J = 14.2 Hz), 3.24 (brs, 2H)
13C-NMR (100 MHz, CHCl3): δ/ppm = 197.5, 197.1, 194.7, 151.5, 150.4, 139.9, 136.3, 133.6, 132.4, 131.7, 130.7, 129.4, 129.3, 128.9, 128.4, 128.3, 127.1, 125.9, 124.6, 124.0, 68.9, 40.7
IR (KBr): 𝑣̃ (cm-1) = 3063, 1681, 1664, 1344, 1210, 700.
HRMS (ESI) for C38H2879BrNO5Na, [M+Na]+ (680.1049), found 680.1042.
HRMS (ESI) for C38H2881
BrNO5Na, [M+Na]+ (682.1028), found 682.1030.
126
(Z)-2,2-dibenzyl-5-(4-bromophenyl)-6-(2-chlorophenyl)-1-phenylhex-4-ene-1,3,6-t rione (83ae)
Prepared according to TP 1 from 79a (50.9 mg, 0.1 mmol), Bu3P (33.0 μL, 1.2 equiv), 2-chlorobenzoyl chloride 72e (14.2 μL, 1.1 equiv), Et3N (17.0 μL, 1.2 equiv) in CH2Cl2. [reaction condition: 30 ℃ for 1 h]. Purification by flash chromatography (SiO2, hexanes: EtOAc, 10:1) furnished 83ae as white solid (27.9 mg, 43%).
m.p: 157.1-157.4 ℃; Rf : 0.51 (hexanes: EtOAc, 10:1)
1H-NMR (400 MHz, CDCl3): δ/ppm = 7.76 (d, 2H, J = 7.8 Hz), 7.64 (d, 1H, J = 7.8 Hz), 7.54-7.44 (m, 3H), 7.41 (t, 2H, J = 7.5 Hz), 7.33 (d, 1H, J = 7.7 Hz), 7.29 (d, 2H, J = 8.2 Hz), 7.23-7.14 (m, 6H), 7.10-6.99 (m, 4H), 6.74 (d, 2H, J = 8.2 Hz), 5.79 (s,
1H), 3.57 (d, 2H, J = 14.2 Hz), 3.25 (d, 2H, J = 14.2 Hz)
13C-NMR (100 MHz, CHCl3): δ/ppm = 197.6, 197.2, 194.2, 153.1, 136.3, 136.0, 134.2, 133.6, 133.5, 133.3, 132.5, 132.4, 132.1, 131.9, 130.8, 129.4, 128.8, 128.7, 128.2, 126.9, 126.6, 125.3, 124.0, 69.0, 40.9
IR (KBr): 𝑣̃ (cm-1) = 3063, 3028, 1664, 1578, 1488, 738, 699.
HRMS (ESI) for C38H2979Br35ClO3, [M+H]+ (647.0989), found 647.0988; [M+2]+ (649.0968), found 649.0970; [M+4]+ (651.0939), found 651.0957.
127
2-Benzyl-2-(4-(4-bromophenyl)-5-phenylfuran-2-yl)-1,3-diphenylpropan-1-one (84aa)
Prepared according to TP 1 from 79a (50.9 mg, 0.1 mmol), Bu3P (33.0 μL, 1.2 equiv), benzoyl chloride 72a (13.0 μL, 1.1 equiv) and Et3N (17.0 μL, 1.2 equiv) in CH2Cl2 (0.5 mL) [reaction condition: 30 °C for 13 h]. Purification by flash chromatography (EtOAc/hexanes: 1/10) furnished 84aa as a white solid .
1H-NMR (400 MHz, CDCl3) δ/ppm: 7.63 (d, 2H, J = 7.5 Hz), 7.48 (d, 2H, J = 8.6 Hz), 7.42 (t, 1H, J = 7.3 Hz), 7.29 (t, 2H, J = 7.7 Hz), 7.25-7.19 (m, 7H), 7.19-7.15 (m, 6H), 6.96-6.91 (m, 4H), 6.23 (s, 1H), 3.51 (d, 2H, J = 14.1 Hz), 3.44 (d, 2H, J = 14.1 Hz)
13C-NMR (100 MHz, CDCl3) δ/ppm: 199.8, 154.2, 147.8, 137.7, 136.6, 133.1, 132.0, 131.8, 130.5, 130.4, 130.2, 129.0, 128.3, 128.2, 127.9, 127.7, 126.6, 126.1, 122.0, 121.2, 112.0, 57.8, 41.2.
HRMS (ESI) for C38H3079BrO2, [M+H]+ (597.1429), found 597.1428.
128
(E)-5-(4-bromophenyl)-2,2-Dimethyl-1-phenylpent-4-ene-1,3-dione (96a)
Prepared according to General procedure B from 105a (1.650 g, 5 mmol), K2CO3
(4.20 g, 6 equiv.), and MeI (1.25 mL, 4 equiv.) in acetone (10.0 mL) and stirred for another 1 day] Purification by flash chromatography (EtOAc/hexanes: 1/10) furnished the desired product 96a as a white solid (1.2 g, 68%).
m.p: 61.2-62.5 ℃; Rf : 0.75 (hexanes: EtOAc, 5:1)
1H-NMR (400 MHz, CDCl3) δ/ppm: 7.81 (d, 2H, J = 7.5 Hz), 7.67 (d, 1H, J = 15.4 Hz), 7.49 (t, 1H, J = 7.5 Hz), 7.46 (d, 2H, J = 8.4 Hz), 7.38 (t, 2H, J = 7.7 Hz), 7.30 (d, 2H, J = 8.4 Hz), 6.66 (d, 1H, J = 15.4 Hz), 1.55 (s, 3H)
13C-NMR (100 MHz, CDCl3) δ/ppm: 199.8, 198.5, 143.1, 135.7, 133.0, 132.1, 129.9, 129.1, 128.6, 125.1, 122.1, 60.3, 23.1
129
(Z)-5-(4-bromophenyl)-2,2-Dimethyl-1,6-diphenylhex-4-ene-1,3,6-trione (97aa)
Prepared according to TP 1 from 96a (35.7 mg, 0.1 mmol), Bu3P (33.0 μL, 1.2 equiv), benzoyl chloride 72a (13.0 μL, 1.1 equiv) and Et3N (17.0 μL, 1.2 equiv) in THF (0.50 mL) [reaction condition: 30 °C for 1 h]. Purification by flash chromatography (EtOAc/hexanes: 1/10) furnished 97aa as a white solid. (27.7 mg, 60%).
m.p: 147.3-148.3 ℃; Rf : 0.50 (hexanes: EtOAc, 5:1)
1H-NMR (400 MHz, CDCl3) δ/ppm: 7.81 (d, 2H, J = 7.5 Hz), 7.74 (d, 2H, J = 7.5 Hz), 7.59 (t, 1H, J = 7.5 Hz), 7.55 (t, 1H, J = 8.8 Hz), 7.47-7.36 (m, 6H), 7.18 (d, 2H, J = 8.8 Hz), 6.63 (s, 1H), 1.48 (s, 3H)
13C-NMR (100 MHz, CDCl3) δ/ppm: 199.4, 197.2, 196., 155.2, 135.7, 135.4, 133.7, 133.2, 132.3, 129.1, 128.9, 128.8, 128.6, 128.5, 125.7, 121.0, 60.3, 22.8
130
Ethyl (E)-5-(4-bromophenyl)-2,2-dimethyl-3-oxopent-4-enoate (96b)
Prepared according to General procedure C.
m.p: 54.7-55.4 ℃; Rf : 0.70 (hexanes: EtOAc, 5:1)
1H-NMR (400 MHz, CDCl3) δ/ppm: 7.64 (d, 1H, J = 15.9 Hz), 7.52 (d, 2H, J = 8.4 Hz), 7.40 (d, 2H, J = 8.4 Hz), 6.84 (d, 1H, J = 15.9 Hz), 4.20 (q, 2H, J = 7.5 Hz), 1.45 (s, 3H), 1.22 (t, 3H, J = 7.1 Hz)
13C-NMR (100 MHz, CDCl3) δ/ppm: 196.2, 173.7, 142.3, 133.3, 132.1, 129.8, 129.7, 121.5, 61.3, 54.7, 21.8, 14.0
131
Ethyl (Z)-5-(4-bromophenyl)-2,2-dimethyl-3,6-dioxo-6-phenylhex-4- Enoate (97ba)
Prepared according to TP 1 from 96b (32.5 mg, 0.1 mmol), Bu3P (31.0 μL, 1.1 equiv), benzoyl chloride 72a (13.0 μL, 1.1 equiv) and Et3N (17.0 μL, 1.2 equiv) in THF (0.50 mL) [reaction condition: 27-30 °C for 1 h]. Purification by flash chromatography (EtOAc/hexanes: 1/10) furnished 97ba as a white solid (10.9 mg, 31%).
m.p: 244.2-245.1 ℃; Rf : 0.58 (hexanes: EtOAc, 5:1)
1H-NMR (400 MHz, CDCl3) δ/ppm: 7.89 (d, 2H, J = 7.1 Hz), 7.55 (t, 1H, J = 7.5 Hz), 7.50 (d, 2H, J = 8.4 Hz), 7.43 (t, 1H, J = 7.7 Hz), 7.35 (d, 2H, J = 8.8 Hz), 6.72 (s, 1H), 4.43 (q, 2H, J = 7.1 Hz), 1.36 (s, 3H), 1.28 (t, 3H, J = 7.1 Hz)
13C-NMR (100 MHz, CDCl3) δ/ppm: 196.7, 195.2, 173.5, 135.4, 133.6, 13.2, 132.4, 128.8, 128.6, 128.5, 125.4, 121.1, 61.6, 54.7, 21.6, 14.1
IR (KBr) 𝑣̃ (cm-1): 1736, 1689, 1678, 688.
132
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2011, 50, 7337-7341.
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