supporting information · typical procedure for the decarboxylation of madelic acid with acrylate a...

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: leiwang@chnu.edu.cnb 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

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16

17

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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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