Electronic Supplementary Material (ESI) for Green Chemistry This journal is © The Royal Society of Chemistry 2012
Copper-Catalyzed C-C Bond Cleavage and Intramolecular Cyclization: An Approach toward Acridones
Supporting Information
Wang Zhou,*,a Youqing Yang,a Yong Liu,b Guo-Jun Dengb a
College of Chemical Engineering, Xiangtan University, Xiangtan 411105, China b
College of Chemistry, Xiangtan University, Xiangtan 411105, China
E-mail:
[email protected]
Contents: General Remarks.........................................................................................................S2 Experimental Section…………………………………………
………………….S3
Analytical Data for Compounds 2.............................................................................S15 References..................................................................................................................S26 NMR and HRMS Spectra…………………………………………..........................S27
S1
Electronic Supplementary Material (ESI) for Green Chemistry This journal is © The Royal Society of Chemistry 2012
General Remarks All manipulations were conducted with a standard Schlenk technique. We removed the plug of stopcock on Schlenk tube when the reaction was carried out under air. 1
H-NMR spectra were recorded on a Bruker AVIII-400 spectrometer. Chemical shifts
(in ppm) were referenced to tetramethylsilane (δ = 0 ppm) in DMSO-d6 as an internal standard. 13C-NMR spectra were obtained by using the same NMR spectrometers and calibrated with DMSO-d6 (δ = 39.60 ppm). Mass spectra were recorded using an Agilent 5975 GC-MS. Unless otherwise noted, materials obtained from commercial suppliers were used without further purification.
S2
Electronic Supplementary Material (ESI) for Green Chemistry This journal is © The Royal Society of Chemistry 2012
Experimental Section 1) Typical procedure A Schlenk tube was charged with substrate 1 (0.3 mmol), CuI (0.06 mmol) and mixed solvent (vDMSO/vPhCl = 1:1, 1.6 mL). The mixture was stirred at 140 oC under air for 48 hours and monitored by TLC. The reaction was cooled down to room temperature, diluted with ethyl acetate (150 mL) due to the poor solubility of desired products, washed with brine (3×20 mL), dried over anhydrous Na2SO4, filtered, and dried under vaccum. The crude product was purified by column chromatography on silica gel to obtain the desired products 2.
2) Table S1 Table S1 The transformation using DMSO as solvent
a
O O
Me CuI (20 mol%) NH
R
DMSO, 140 oC, air N H
R 1 Entry O
85
1a Me
32 1b
Me
49 1c
N H 2c
Me
6
OMe
2d
O
1f O
3
44 N H
H N
N H 2b
Me
OMe
Me
5
O H N
H N
O
Me
2
Me
O
1d
H N
O
Me
4
N H 2a O
Yield (%)b
Product
Substrate O
H N
O
Entry
O
Me
1
a
2 Yield (%)b
Product
Substrate
Ph 21 Ph
Me
N H 2f O
H N
1i
Cl 39 Cl
N H
2i
o
Reaction conditions: substrate 1 (0.30 mmol), CuI (20 mol%) in DMSO (1.6 mL) were stirred at 140 C under air for b
36 h. Isolated yield.
S3
Electronic Supplementary Material (ESI) for Green Chemistry This journal is © The Royal Society of Chemistry 2012
3) Table S2 Table S2 Optimization of reaction conditions using 1d as substrate O
Me
O H N
CuI (20 mol%) solvent, 140 oC, OMe
N H
36 h, air
1d
OMe 2d
Entry
Yield of 2d (%)b
Additive (equiv.)
1 2c
44
----FeCl2 (0.1) ZnCl2 (0.1)
3 4
40 56 41 49
AlCl3 (0.1) TsOH (0.1)
5 6 7
L-proline (0.4)
55 58
8 9d
H2O (3.0) ---
10
