supporting information · typical procedure for the decarboxylation of madelic acid with acrylate a...
TRANSCRIPT
Supporting Information
Ru-catalyzed decarboxylative cyclization of mandelic acids with acrylates:
facile access to phthalide skeleton
Lili Chen,a Hongji Li,*a Feng Yu,a and Lei Wang *a,b
a Department of Chemistry, Huaibei Normal University, Huaibei, Anhui 235000, P R China, Tel: +86-
561-3802-069 Fax: +86-561-3090-518 E-mail: [email protected] State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese
Academy of Sciences, Shanghai 200032, P R China
Table of Contents for Supporting Information
1. General considerations….….….….…………………….……….….…………………………………1
2. Typical procedure for the decarboxylation of madelic acid with acrylate………….………………….1
3. Effect of solvent on the Ru-catalyzed decarboxylative reaction….….….….…...………….………2
4. FT-IR analysis of the resulting gas in Ru-catalyzed decarboxylative reaction….…….……………2
5. HRMS spectra for mechanistic study…….….…….…….……......…..…..…….….…….…………3
6. Procedure for the control experiments.….…..….….….…….….………………………………………3
7. Characterization data for the products.….…..….….….…….….………………………………………3
8. 1H and 13C NMR spectra of the products…..…….….…….….………………………………………11
9. References….….….….….….….….….….….….….….…….….………………………………………33
Electronic Supplementary Material (ESI) for ChemComm.This journal is © The Royal Society of Chemistry 2014
1. General considerations
All 1H NMR and 13C NMR spectra were recorded on a 400 MHz Bruker FT-NMR spectrometers
(400 MHz or 100 MHz, respectively). All chemical shifts are given as δ value (ppm) with reference to
tetramethylsilane (TMS) as an internal standard. The peak patterns are indicated as follows: s, singlet; d,
doublet; t, triplet; m, multiplet; q, quartet. The coupling constants, J, are reported in Hertz (Hz). High
resolution mass spectroscopy data of the product were collected on a Waters Micromass GCT instrument.
High resolution mass spectroscopy data of the product were collected on an Agilent Technologies 6540
UHD Accurate-Mass Q-TOF LC/MS (ESI).
Mandelic acids are prepared from aromatic laldehydes,1-2 and which must be recrystallized from
ethanol/ethyl acetate before use. The chemicals and solvents were purchased from commercial suppliers
either Shanghai Chemical Company, China, or Aldrich, USA. All the solvents were dried and freshly
distilled in N2 prior to use. Products were purified by flash chromatography on 200–300 mesh silica gels,
SiO2.
2. Typical procedure for the decarboxylation of madelic acid with acrylate
A 10 mL of reaction tube was charged with 2-hydroxy-2-phenylacetic acid (1a, 0.20 mmol, excess),
ethyl acrylate (2a, 0.20 mmol), [Ru(p-cymene)Cl2]2 (6.0 mg, 0.01 mmol), Cu(OAc)2 (40.0 mg, 0.22
mmol,1.1 equiv) and DMF (1.0 mL). The reaction vessel was placed in an oil bath. After the reaction
was carried out at 110 oC for 12 h, it was cooled to room temperature, extracted with EtOAc (3×5.0 mL).
The organic layers were combined, dried over MgSO4, and concentrated to yield the crude product, which
was further purified by flash chromatography (silica gel, petroleum ether/ethyl acetate= 9:1 to 3:1) to give
the desired product 3aa (22.3 mg, 70%).
1
3. Effect of solvent on the Ru-catalyzed decarboxylative reaction
Table S1 Effect of the solvent on the decarboxylative reaction of 2-hydroxy-2-phenylacetic acid (1a) with ethyl acrylate (2a)a
1a 2a 3aa
COOEt
OH
COOH
[Ru] (5.0 mol%)Cu(OAc)2 (1.1 equiv)
O
O
COOEt
solvent, 110 C, air, 12 h
COOEt
entry solvent yield(%)a
1 DCE n.r.
2 Toluene n.r.
3 1,4-dioxane trace
4 THF trace
5 H2O n. r.
6 Acetic acid n. r.
7 DMSO 17
8 DMF 70
9 DMA 45a Reaction conditions: 2-hydroxy-2-phenylacetic acid (1a, 0.20 mmol, excess), ethyl acrylate (2a, 0.20 mmol), [Ru] = [Ru(p-cymene)Cl2]2 (0.01 mmol, containing Ru 5.0 mol%), Cu(OAc)2 (0.22 mmol, 1.1 equiv), solvent (1.0 mL) at 110 ºC in air for 12 h. b Isolated yield. n.r. = no reaction.
4. FT-IR analysis of the resulting gas in Ru-catalyzed decarboxylative reaction
Figure S1 FT-IR analysis of the resulting gas during the reaction
2
5. HRMS spectra for mechanistic study
5x10
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
+ESI Scan (0.248-0.348 min, 10 Scans) Frag=180.0V demo1.d
332.0810
301.1074
299.0530307.0969
319.1178
Counts vs. Mass-to-Charge (m/z)298 300 302 304 306 308 310 312 314 316 318 320 322 324 326 328 330 332 334
OH
O
COOEt
COOEt
VI
H+
HRMS (ESI) ([M+H]+)m/z : calcd. for C17H19O16: 319.1182,found: 319.1178
VI
Figure S2 HRMS spectra of intermediate VI
6. Procedure for control experiment (2-oxo-2-phenylacetic acid as typical example)
A 10 mL of reaction tube was charged with 2-oxo-2-phenylacetic acid (0.20 mmol), ethyl acrylate
(2a, 0.20 mmol), [Ru(p-cymene)Cl2]2 (6.0 mg, 0.01 mmol), Cu(OAc)2 (40.0 mg, 0.22 mmol, 1.1 equiv)
and DMF (1.0 mL). The reaction vessel was placed in an oil bath. After the reaction was carried out at
110 oC for 12 h, it was cooled to room temperature, extracted with EtOAc (3×5.0 mL). The organic layers
were combined, dried over MgSO4, and concentrated to yield the crude product, which was further
purified by flash chromatography (silica gel, petroleum ether/ethyl acetate= 9:1 to 3:1) to give the desired
product 3aa (9.2 mg, 29%).
7. Characterization data for the products
O
O
COOEt
COOEt
3aa:3 δ: 8.68 (d, J = 16.0 Hz, 1H), 7.76 (d, J = 7.6 Hz, 1H), 7.67 (t, J = 7.1 Hz, 1H), 7.49 (d, J = 7.6 Hz,
1H), 6.59 (d, J = 16.0 Hz, 1H), 5.84 (t, J = 6.4 Hz, 1H), 4.28 (q, J = 7.2 Hz, 2H), 4.19 (q, J = 7.2 Hz, 2H),
2.90 (d, J = 6.4 Hz, 2H), 1.34 (t, J = 7.2 Hz, 3H), 1.25 (t, J = 7.2 Hz, 3H); 13CNMR (100 MHz, CDCl3) δ:
169.05, 168.84, 166.02, 149.62, 137.17, 134.90, 134.18, 126.56, 123.05, 122.96, 122.92, 75.96, 61.22,
60.72, 39.33, 14.17, 13.99. HRMS (EI) ([M]+) Calcd. for C17H18O6: 318.1103, Found: 318.1099.
3
O
O
COOMe
COOMe
3ab: 1H NMR (400 MHz, CDCl3) δ: 8.70 (d, J = 16.0 Hz, 1H), 7.77 (d, J = 7.6 Hz, 1H), 7.68 (t, J = 7.6
Hz, 1H), 7.50 (d, J = 7.6 Hz, 1H), 6.60 (d, J = 16.0 Hz, 1H), 5.86 (t, J = 6.4 Hz,1H), 3.83 (s, 3H), 3.76 (s,
3H), 2.91 (d, J = 6.4 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ: 169.52, 168.77, 166.43, 149.55, 137.38,
134.84, 134.24, 126.61, 123.02, 122.49, 75.92, 52.17, 51.86, 39.14. HRMS (EI) ([M]+) Calcd. for
C15H14O6: 290.0790, Found: 290.0787.
O
O
COOnBu
COOnBu
3ac:3 1H NMR (400 MHz, CDCl3) δ: 8.71 (d, J = 16.0 Hz 1H), 7.77 (d, J = 7.6 Hz 1H), 7.67 (t, J = 7.6
Hz , 1H), 7.49 (d, J = 7.6 Hz 1H), 6.60 (d, J = 16.0 Hz 1H), 5.85 (t, J = 6.4 Hz 1H), 4.27 (q, J = 6.8 Hz,
2H), 4.18 (q, J = 6.8 Hz, 2H), 2.93–2.90 (m, 2H), 1.74–1.67 (m, 2H), 1.64–1.57 (m, 2H), 1.48–1.40 (m,
2H), 1.38–1.33 (m, 2H), 1.00–0.91 (m, 6H); 13C NMR (100 MHz, CDCl3) δ: 169.09, 168.78, 166.08,
149.64, 137.18, 134.97, 134.11, 126.55, 123.10, 122.95, 122.89, 75.94, 65.10, 64.61, 39.34, 30.59, 30.38,
19.05, 18.92, 13.60, 13.51. HRMS (EI) ([M]+) Calcd. for C21H26O6: 374.1729, Found: 374.1730.
O
O
COOtBu
COOtBu
3ad: 1H NMR (400 MHz, CDCl3) δ: 8.63 (d, J = 16.4 Hz, 1H), 7.75 (d, J = 7.6 Hz 1H), 7.65 (d, J = 7.2
Hz, 1H), 7.47 (d, J = 7.6 Hz, 1H), 6.53 (d, J = 16.0 Hz, 1H), 5.79 (t, J = 6.4 Hz, 1H), 2.86–2.82 (m, 2H),
1.55 (s, 9H), 1.44 (s, 9H); 13C NMR (100 MHz, CDCl3) δ: 168.94, 168.19, 165.32, 149.81, 148.90,
136.32, 133.97, 126.36, 122.67, 81.91, 80.85, 76.14, 40.47, 40.42, 29.56, 28.02, 27.87. HRMS (EI)
([M]+) Calcd. for C21H26O6: 374.1729, Found: 374.1726.
4
O
O
O O
CH3
O
O
(CH2)5 CH3
CH3
(CH2)5CH3
3ae: 1H NMR (400 MHz, CDCl3) δ: 8.74 (d, J = 16.0 Hz, 1H), 7.79 (d, J = 7.6 Hz, 1H), 7.67 (t, J = 7.6
Hz, 1H), 7.50 (d, J = 7.6 Hz, 1H), 6.61 (d, J = 16.0 Hz, 1H), 5.86 (t, J = 6.4 Hz, 1H), 4.15–4.07 (m, 4H),
2.99–2.86 (m, 2H), 1.71–1.57 (m, 4H), 1.45–1.27 (m, 20H), 0.95–0.89 (m, 6H); 13C NMR (100 MHz,
CDCl3) δ: 169.34, 168.85, 166.29, 149.70, 137.24, 134.04, 134.17, 126.60, 123.17, 122.97, 75.99, 67.72,
67.21, 39.44, 38.77, 30.40, 30.25, 28.91, 28.83, 23.80, 23.61, 23.58, 22.95, 22.89, 14.04, 14.02, 11.01,
10.91, 10.90. HRMS (EI) ([M]+) Calcd. for C29H42O6: 486.2981, Found: 486.2986.
O
O
O OCH2Ph
O
OCH2Ph
3af: 1H NMR (400 MHz, CDCl3) δ: 8.76 (d, J = 16.0 Hz, 1H), 7.75 (d, J = 7.6 Hz, 1H), 7.62 (t, J = 7.2
Hz, 1H), 7.46–7.35 (m, 11H), 6.64 (d, J = 16.4 Hz, 1H), 5.86 (t, J = 6.4 Hz, 1H), 5.30 (s, 2H), 5.23–5.16
(m, 2H), 3.04–2.90 (m, 2H); 13C NMR (100 MHz, CDCl3) δ: 168.81, 168.66, 165.76, 149.49, 137.81,
135.84, 135.03, 134.84, 134.11, 128.55, 128.48, 128.46, 128.39, 128.13, 128.12, 126.61, 123.14, 122.99,
122.54, 75.82, 67.03, 66.42, 39.33. HRMS (ESI) ([M+H]+) Calcd. for C27H22O6: 442.1416, Found:
442.1617.
O
O
COOCH2CH2OPh
COOCH2CH2OPh
3ag: 1H NMR (400 MHz, CDCl3) δ: 8.75 (d, J = 16.4 Hz, 1H), 7.74 (d, J = 7.6 Hz, 1H), 7.63 (t, J = 7.6
Hz, 1H), 7.51 (d, J = 7.6 Hz, 1H), 7.33–7.28 (m, 4H), 6.70–6.95 (m, 4H), 6.90–6.89 (m, 2H), 6.63 (d, J =
16.4 Hz, 1H), 5.86 (t, J = 6.4 Hz, 1H), 4.60 (t, J = 4.8 Hz, 2H), 4.53 (t, J = 2.4 Hz, 2H), 4.27 (t, J = 4.8
5
Hz, 2H), 4.18 (t, J = 4.4 Hz, 2H), 3.00–2.96 (m, 2H); 13C NMR (100 MHz, CDCl3) δ: 168.89, 168.68,
165.85, 158.39, 158.18, 149.47, 137.94, 134.75, 134.18, 129.45, 129.42, 126.68, 123.14, 123.09, 122.27,
121.23, 121.07, 114.62, 114.48, 75.75, 65.79, 65.44, 63.52, 63.06, 39.17. HRMS (EI) ([M]+) Calcd. for
C29H26O8: 502.1633, Found: 502.1632.
3ah: 1H NMR (400 MHz, CDCl3) δ: 8.93 (d, J = 16.4 Hz, 1H), 7.88 (d, J = 7.6 Hz, 1H), 7.75 (t, J = 7.6
Hz, 1H), 7.61 (d, J = 7.2 Hz, 1H), 7.45–7.39 (m, 4H), 7.29–7.25 (m, 2H), 7.21 (d, J = 8.0 Hz, 2H), 7.11 (d,
J = 7.2 Hz, 2H), 6.82 (d, J = 16.4 Hz, 1H), 5.98 (t, J = 6.4 Hz, 1H), 3.22–3.20 (m, 2H); 13C NMR (100
MHz, CDCl3) δ: 168.63, 167.61, 164.38, 150.64, 150.12, 149.45, 138.99, 134.71, 134.36, 129.46, 129.31,
126.99, 126.17, 125.75, 123.39, 123.34, 122.20, 121.48, 121.22, 75.75, 39.39. HRMS (EI) ([M]+) Calcd.
for C25H18O6: 414.1103, Found: 414.1105.
3ai: 1H NMR (400 MHz, CDCl3) δ: 8.92 (d, J = 16.0 Hz, 1H), 7.88 (d, J = 7.6 Hz, 1H), 7.76 (t, J = 7.6
Hz,1H), 7.61 (d, J = 7.6 Hz, 1H), 7.38 (dd, J = 8.4 Hz, J = 6.0 Hz, 4H), 7.16 (d, J = 8.4 Hz, 2H), 7.06 (d,
J = 8.8 Hz, 2H), 6. 80 (d, J = 16.0 Hz, 1H), 5.97 (t, J = 6.4 Hz, 1H), 3.20 (d, J = 6.8 Hz, 2H); 13C NMR
(100 MHz, CDCl3) δ: 168.50, 167.33, 164.05, 149.30, 149.08, 148.52, 139.30, 134.63, 134.39, 131.65,
131.15, 129.53, 129.37, 127.08, 123.38, 122.84, 122.58, 121.87, 75.62, 39.32. HRMS (EI) ([M]+) Calcd.
for C25H17O6Cl: 482.0324, Found: 482.0329.
O
O
COOEt
COOEt
Me
3ba: 1H NMR (400 MHz, CDCl3) δ: 8.65 (d, J = 16.4 Hz, 1H), 7.57 (s, 1H), 6.60 (d, J = 16.4 Hz, 1H),
5.81 (t, J = 6.4 Hz, 1H), 4.29 (q, J = 7.2 Hz, 2H), 4.22 (q, J = 7.2 Hz, 2H), 2.89 (t, J = 6.0 Hz, 2H), 2.50
6
(s, 3H), 1.35 (t, J = 7.2 Hz, 3H), 1.28 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ: 169.16, 168.84,
166.08, 150.15, 145.39, 137.35, 134.57, 127.58, 123.41, 122.69, 120.69, 75.73, 61.21, 60.69, 39.44, 21.97,
14.18, 14.02. HRMS (EI) ([M]+) Calcd. for C18H20O6: 332.1262, Found: 332.1264.
O
O
COOEt
COOEt
Et
3ca: 1H NMR (400 MHz, CDCl3) δ: 8.64 (d, J = 16.4 Hz, 1H), 7.58 (s, 1H), 7.29 (s, 1H), 6.60 (d, J = 16.0
Hz, 1H), 5.81 (t, J = 6.4 Hz, 1H), 4.29 (q, J = 7.2 Hz, 2H), 4.21 (q, J = 7.2 Hz, 2H), 2.96–2.88 (m, 2H),
2.85–2.75 (m, 2H), 1.36–1.25 (m, 9H); 13C NMR (100 MHz, CDCl3) δ: 169.11, 168.78, 166.05, 151.59,
150.23, 137.46, 134.70, 126.54, 122.67, 122.22, 120.90, 75.79, 61.14, 60.63, 39.49, 29.16, 15.05, 14.15,
13.99. HRMS (EI) ([M]+) Calcd. for C19H22O6: 346.1419, Found: 346.1419.
O
O
COOEt
COOEt
i-Pr
3da: 1H NMR (400 MHz, CDCl3) δ: 8.65 (d, J = 16.4 Hz, 1H), 7.61 (s, 1H), 7.32 (s, 1H), 6.62 (d, J =
16.4 Hz, 1H), 5.82 (t, J = 6.4 Hz, 1H), 4.29 (q, J = 7.2 Hz, 2H), 4.22 (q, J = 7.2 Hz, 2H), 3.04 (t, J = 6.8
Hz, 1H), 2.90 (t, J = 6.0 Hz, 2H), 1.37–1.26 (m, 12H); 13C NMR (100 MHz, CDCl3) δ: 169.13, 168.77,
166.08, 156.27, 150.23, 137.58, 134.76, 125.29, 122.67, 121.05, 120.81, 75.87, 61.15, 60.65, 39.57, 34.57,
23.62, 23.53, 14.16, 14.01. HRMS (EI) ([M]+) Calcd. for C20H22O6: 360.1573, Found: 360.1570.
O
O
COOEt
COOEt
MeO
3ea: 1H NMR (400 MHz, CDCl3) δ: 8.61 (d, J = 16.0 Hz,1H), 7.23 (s, 1H), 6.96 (s, 1H), 6.58 (d, J = 16.0
Hz, 1H), 5.78 (t, J = 6.4 Hz, 1H), 4.29 (q, J = 7.2 Hz, 2H), 4.20 (q, J = 7.2 Hz, 2H), 3.92 (s, 3H), 2.97–
2.82 (m, 2H), 1.35 (t, J = 7.2 Hz, 3H), 1.28 (t, J = 7.2 Hz, 3H); 13CNMR (100MHz, CDCl3) δ: 169.17,
168.53, 165.96, 164.39, 152.36, 137.30, 136.37, 123.08, 115.75, 113.08, 107.63, 75.49, 61.20, 60.73,
55.86, 39.49, 14.15, 14.01. HRMS (EI) ([M]+) Calcd. for C18H20O7: 348.1209, Found: 348.1205.
7
O
O
COOEt
COOEt
F
3fa: 1H NMR (400 MHz, CDCl3) δ: 8.62 (d, J = 16.4 Hz, 1H), 7.42 (d, J = 8.4 Hz, 1H), 7.21 (d, J = 6.8
Hz, 1H), 6.57 (d, J = 16.4 Hz, 1H), 5.81 (t, J = 6.4 Hz, 1H), 4.29 (q, J = 7.2 Hz, 2H), 4.21 (q, J = 7.2 Hz,
2H), 3.01–2.83 (m, 2H), 1.34 (t, J = 7.2 Hz, 3H), 1.27 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ:
168.85, 167.72, 166.26 (d, JC-F = 255.4 Hz), 165.58, 152.50 (d, JC-F = 10.4 Hz), 137.50 (d, JC-F = 9.3 Hz),
136.04 (d, JC-F = 4.0 Hz), 124.16, 119.30, 114.22 (d, JC-F = 24.2 Hz), 110.60 (d, JC-F = 24.8 Hz), 75.54 (d,
JC-F = 2.6 Hz), 61.33, 60.88, 39.03, 14.11, 13.97. HRMS (EI) ([M]+) Calcd. for C17H17O6F: 336.1009,
Found: 336.1008.
O
O
COOEt
COOEt
Cl
3ga:1H NMR (400 MHz, CDCl3) δ: 8.60 (d, J = 16.0 Hz, 1H), 7.73 (s, 1H), 7.50 (s, 1H), 6.59 (d, J =
16.4 Hz, 1H), 5.82 (t, J = 6.4 Hz,1H), 4.29 (q, J = 6.8 Hz, 2H), 4.22 (q, J = 6.8 Hz, 2H), 3.01–2.84 (m,
2H), 1.35 (t, J = 7.2 Hz, 3H), 1.28 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ: 168.80, 167.76,
165.55, 151.26, 140.82, 136.27, 135.89, 126.94, 124.18, 123.24, 121.58, 75.52, 61.34, 60.86, 39.02, 14.12,
13.98. HRMS (EI) ([M]+) Calcd. for C17H17O6Cl: 352.0714, Found: 352.0710.
O
O
COOEt
COOEt
Br
3ha: 1H NMR (400 MHz, CDCl3) δ: 8.59 (d, J = 16.4 Hz, 1H), 7.90 (s, 1H), 7.67 (s, 1H), 6.59 (d, J =
16.0 Hz, 1H), 5.82 (d, J = 6.4 Hz, 1H), 4.30 (q, J = 7.2 Hz, 2H), 4.23 (q, J = 7.2 Hz, 2H), 3.01–2.84 (m,
2H), 1.35 (t, J = 7.2 Hz, 3H), 1.28 (t, J = 7.2 Hz, 3H); 13CNMR (100 MHz, CDCl3) δ: 168.78, 167.89,
165.54, 151.30, 136.37, 135.83, 129.86, 129.25, 126.20, 124.23, 122.03, 75.45, 61.35, 60.86, 39.04,
14.12, 13.98. HRMS (EI) ([M]+) Calcd. for C17H17O6Br: 396.0208, Found: 396.0206.
8
O
O
COOEt
COOEt
F3C
3ia: 1H NMR (400 MHz, CDCl3) δ: 8.67 (d, J = 16.4 Hz, 1H), 8.00 (s, 1H), 7.78 (s, 1H), 6.67 (d, J = 16.4
Hz, 1H), 5.91 (t, J =6.4 Hz, 1H), 4.30 (q, J = 7.2 Hz, 2H), 4.21 (q, J = 7.2 Hz, 2H), 3.06–2.90 (m, 2H),
1.35 (t, J = 7.2 Hz, 3H), 1.27 (t, J = 7.2 Hz, 3H); 13CNMR (100 MHz, CDCl3) δ: 168.68, 167.46, 165.44,
150.28, 136.24, 135.96, 135.80 (d, JC-F = 20.1 Hz), 125.98 (q, JC-F = 0.9 Hz), 123.70 (q, JC-F = 3.6 Hz),
123.10 (q, JC-F = 272.1 Hz), 121.50, 119.92, 75.96, 61.39, 60.94, 38.88, 14.10, 13.93. HRMS (EI) ([M]+)
Calcd. for C18H17O6F3: 386.0977, Found: 386.0976.
O
O
COOEt
COOEt
Ph
3ja: 1H NMR (400 MHz, CDCl3) δ: 8.72 (d, J = 16.4 Hz, 1H), 7.96 (s, 1H), 7.67–7.47 (m, 7H), 6.70 (d, J
= 16.0 Hz, 1H), 5.92 (t, J = 6.4 Hz, 1H), 4.31 (q, J = 7.2 Hz, 2H), 4.23 (q, J = 7.2 Hz, 2H), 3.02–2.91 (m,
2H), 1.37 (t, J = 7.2 Hz, 3H), 1.28 (t, J = 7.2 Hz, 3H); 13CNMR (100 MHz, CDCl3) δ: 169.13, 168.76,
165.99, 150.51, 147.61, 138.91, 137.30, 135.07, 129.11, 128.89, 127.37, 125.82, 123.07, 121.76, 121.45,
76.00, 61.25, 60.76, 39.39, 14.18, 14.02. HRMS (EI) ([M]+) Calcd. for C23H22O6: 394.1416, Found:
394.1418.
O
O
COOEt
COOEt
3ka: 1H NMR (400 MHz, CDCl3) δ: 8.76 (d, J = 16.4 Hz, 1H), 8.20 (s, 1H), 8.04 (d, J = 7.6 Hz, 1H), 7.87
(d, J = 7.6 Hz, 1H), 7.72 (t, J = 8.0 Hz, 2H), 6.70 (d, J = 16.0 Hz, 1H), 6.26 (dd, J = 8.8 Hz, J = 2.4 Hz,
1H), 4.31 (q, J = 7.2 Hz, 2H), 4.21 (q, J = 7.2 Hz, 2H), 3.38–3.34 (m, 1H), 2.78–2.72 (m, 1H), 1.37 (t, J =
7.2 Hz, 3H), 1.26 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ: 169.26, 168.99, 166.16, 149.09,
137.95, 135.77, 129.90, 129.88, 129.64, 128.70, 127.98, 126.64, 123.27, 122.20, 121.19, 75.91, 61.31,
60.63, 40.00, 14.20, 13.97. HRMS (EI) ([M]+) Calcd. for C21H20O6: 368.1260, Found: 368.1262.
9
O
O
COOEt
COOEt
MeO
OMeMeO
3la: 1H NMR (400 MHz, CDCl3) δ: 8.51 (d, J = 16.4 Hz, 1H), 7.01 (d, J = 16.4 Hz, 1H), 5.77 (dd, J =
8.0 Hz, J = 3.2 Hz, 1H), 4.28 (q, J = 7.2 Hz, 2H), 4.18 (q, J = 7.2 Hz, 2H), 4.05 (s, 3H), 3.98 (s, 3H),
3.89 (s, 3H), 3.20 (dd, J = 16.4 Hz, J = 3.2 Hz, 1H), 2.66 (q, J = 8.0 Hz, 1H), 1.35 (t, J = 7.2 Hz, 3H),
1.25 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ: 169.08, 168.31, 167.21, 155.75, 150.37, 147.90,
136.98, 133.54, 124.81, 123.42, 74.39, 61.06, 61.00, 60.83, 60.45, 60.40, 38.15, 14.18, 13.97. HRMS (EI)
([M]+) Calcd. for C20H24O9: 408.1420, Found: 408.1421.
O
O
COOEt
COOEt
Cl
Cl
3ma: 1H NMR (400 MHz, CDCl3) δ: 8.17 (d, J = 16.4 Hz, 1H), 7.72 (s, 1H), 6.81 (d, J = 16.4 Hz, 1H),
5.80 (dd, J = 7.6 Hz, J = 2.8 Hz, 1H), 4.29 (q, J = 7.2 Hz, 2H), 4.15 (q, J = 7.2 Hz, 2H), 3.40–3.35 (m,
1H), 2.86–2.80 (m, 1H), 1.35 (t, J = 7.2 Hz, 3H), 1.23 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3)
δ: 168.32, 166.46, 165.77, 145.00, 135.92, 135.50, 133.35, 132.39, 128.77, 128.37, 126.99, 74.95, 61.26,
60.90, 36.49, 14.10, 13.93. HRMS (EI) ([M]+) Calcd. for C17H16O6Cl2: 386.0328, Found: 386.0329.
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8. 1H and 13C NMR spectra of the products
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13
14
15
16
17
18
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9. References
[1] Z. Zhang, Z. Wang, R. Zhang and K. Ding, Angew. Chem. Int. Ed., 2010, 49, 6746.
[2] H. Qian, D. Liu and C. Lv, Ultrason. Sonochem., 2011, 18, 1035.
[3] (a) K. Ueura, T. Satoh and M. Miura, J. Org. Chem., 2007, 72, 5362;
(b) K. Ueura, T. Satoh and M. Miura, Org. Lett., 2007, 9, 1407.
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