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Supporting Information
Transition metal-free Suzuki type cross-coupling for synthesis of dissymmetric ketones
Sanjay Jadhava, Gajanan Rashinkara, Rajashri Salunkhea*, Arjun Kumbharb*
aDepartment of chemistry, Shivaji University, Kolhapur, 416006, M.S., India.bP, D. V. P. College, Tasgaon, (Sangali), 416012, M.S., India.
E-mail: [email protected]
Contents:
1. General Remarks
2. General Procedure for the Preparation of DissymmetricKetones
3. Characterization Data for DissymmetricKetones
4. References
5. 1H and 13C Spectra of Dissymmetric Ketones
1. General Remarks
All the chemicals like boronic acids, acyl chlorides, toluene and NaOH were procured from
Sigma Aldrich, Spectrochem, Alfa Aeser chemical firms and used as received without further
purification. All chemicals and reactions were weighed and handled under air atmosphere.1H
NMR and 13C NMR spectra were recorded on a Bruker Avon 200 and 500 MHz spectrometer
using CDCl3 as solvent and tetramethylsilane (TMS) as an internal standard. Chemical shifts (δ)
are reported in ppm, and coupling constants (J) are in Hertz (Hz). Mass spectra were recorded on
Shimadzu QPaltra2010 GC-MS instrument with ion source temperature of 250 °C.
2. General Procedure for the Preparation of Dissymmetric Ketones
An oven-dried Schlenk flask, equipped with a magnetic stir bar, septum and a condenser was
charged with acyl chloride (1.0 mmol), arylboronic acid (1.0 mmol), NaOH (4 mmol) and 5.0
mL of toluene. The flask was immersed and stirred in an oil bath at 100 °C. Upon complete
consumption of starting materials as determined by GC analysis, the water (10.0 mL) was added.
The reaction mixture was extracted with diethyl ether (3 × 5.0 mL). The combined organic layer
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was collected, dried over anhydrous Na2SO4 and concentrated in vacuum to afford product which
was purified by silica gel column chromatography (eluent: n-hexane/ethyl acetate = 9:1 or 8:2).
3. Characterization Data for Dissymmetric Ketones
(4-bromophenyl)(phenyl)methanone (C2): Yellow solid.1H NMR (500 MHz, CDCl3) δ: 7.90
(d, J=8.4 Hz, 1H), 7.83 (d, J=7.2 Hz, 1H), 7.67 (d, J=8.0 Hz, 2H), 7.61 (d, J=8.4 Hz, 2H), 7.51-
7.52 (m, 3H). 13C NMR (126MHz, CDCl3) δ: 195.9, 138.6, 136.3, 132.2, 131.8, 130.5, 129.7,
128.5, 128.01, 126.5. MS (ESI) C13H9OBr: m/z 261.
phenyl(p-tolyl)methanone (C4): Colorless oil.1H NMR (500 MHz, CDCl3) δ:7.78 (d, J= 7.6 Hz,
2H), 7.72 (d, J=8.0 Hz, 2H), 7.57 (t, J=7.4 Hz, 1H), 7.47 (t, J=7.6 Hz, 2H), 7.27-7.29 (m, 2H),
2.44 (s, 3H). 13C NMR (126MHz, CDCl3) δ:196.4, 143.2, 137.9, 134.8, 132.1, 130.2, 129.9,
128.1, 128.2, 21.6. MS (ESI) C14H101OF: m/z 214.
4-chlorophenyl(phenyl)methanone (C5): White solid. 1H NMR (500 MHz, CDCl3)δ: 7.77 (t,
J=8.0 Hz, 4H), 7.60 (m, 1H), 7.45-7.51 (m, 5 H). 13C NMR (126MHz, CDCl3)δ: 195.2, 138.6,
136.9, 135.6, 132.3, 131.1, 129.6, 128.3, 128.1. MS (ESI) C13H9OCl: m/z 216.
(4-cynophenyl)(phenyl)methanone (C6): White solid. 1H NMR (500 MHz, CDCl3)δ:8.33-8.41
(m, 2H), 7.96-7.76 (m, 7H. 13C NMR (126MHz, CDCl3)δ: 193.1, 141.3, 139.6, 132.8, 132.4,
130.7, 130.2, 123.8, 117.6, 116.7. MS (ESI) C14H9ON: m/z 207.
(3,5-dichlorophenyl)(phenyl)methanone (C7): Yellow oil. 1H NMR (500 MHz, CDCl3)δ: 7.77
(d, J=7.6 Hz, 2H), 7.64-7.61 (m, 3H), 7.55 (s, 1H), 7.52-7.49 (m, 2H). 13C NMR (126MHz,
CDCl3) δ:193.6, 140.1, 136.2, 135.2, 133.1, 131.9, 129.9, 128.5, 128.1. MS (ESI) C13H8OCl2:
m/z 250.
phenyl(thiophen-3-yl)methanone (C8): Yellow oil. 1H NMR (500 MHz, CDCl3)δ: 7.91-7.84
(br. s, 1H), 7.83 (d, J=7.6 Hz, 2H), 7.56-7.59 (m, 2H), 7.48-7.47 (m, 2H), 7.46-7.36 (m, 1H). 13C
NMR (126MHz, CDCl3)δ: 189.6, 140.9, 138.2, 133.5, 131.9, 128.9, 128.2, 128.0, 125.8. MS
(ESI) C11H8OS: m/z 188.03.
(4-fluorophenyl)(phenyl)methanone (C9): Colorless oil.1H NMR (500 MHz, CDCl3)δ: 7.85
(dd, J=8.6, 5.5 Hz, 2H), 7.77 (d, J=7.2 Hz, 2H), 7.59 (t, J=7.4 Hz, 1H), 7.49 (t, J=7.6 Hz, 2H),
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7.16 (t, J=8.6 Hz, 2H). 13C NMR (126MHz, CDCl3)δ: 194.9, 166.1 (C-F coupling), 137.2, 133.5,
132.4, 132.1, 129.5, 128.0, 115.0. MS (ESI) C13H9OF: m/z 200.
(4-nitrophenyl)(phenyl)methanone (C10): White solid.1H NMR (500 MHz, CDCl3)δ: 8.35-
8.33 (m, 2H), 7.95-7.93 (m, 2H), 7.80 (d, J= 8.0 Hz, 2H), 7.67-7.64 (m, 1H), 7.54-7.51(m, 2H). 13C NMR (126MHz, CDCl3)δ: 194.5, 149.5, 142.6, 136.0, 133.2, 130.4, 129.8, 128.4, 123.2. MS
(ESI) C13H9NO3: m/z 227.
(4-ethylphenyl)(4-nitrophenyl)methanone (C11): Yellow solid. 1H NMR (200 MHz, CDCl3) δ:
8.36-8.31 (m, 2H), 7.94-7.89 (m, 2H), 7.76-7.72 (m, 2H), 7.36-7.32 (m, 2H), 2.76 (q, J=7.6 Hz,
2H), 1.33-1.25 (m, 3H). 13C NMR (50MHz, CDCl3) δ:194.5, 150.7, 149.6, 143.3, 133.8, 130.5,
130.4, 128.1, 123.4, 29.0, 15.1. MS (ESI) C15H13NO3: m/z 255.
naphthalene-1-yl(4-nitrophenyl)methanone (C12): Yellow oil. 1H NMR (400 MHz, CDCl3)δ:
8.31(d, J=4.00 Hz, 2H), 8.19 (d, J=4.00 Hz, 1H), 8.09 (d, J=4.00 Hz, 1H), 8.01 (d, J=4.00 Hz,
2H), 7.97 (d, J=4.00 Hz, 1H), 7.67-7.53 (m, 4H), 7.46-7.36 (m, 1H). 13C NMR (100 MHz,
CDCl3)δ: 196.00, 150.2, 143.4, 134.7, 133.8, 132.6, 131.2, 129.0, 128.7, 127.9, 126.9, 125.4,
124.3, 123.6. MS (ESI) C17H11O3N: m/z 277.
(4-nitrophenyl)(p-tolyl)methanone (C13): White solid.1H NMR (500 MHz, CDCl3)δ:8.34-8.32
(m, 2H), 7.92-7.90 (m, 2H), 7.72-7.70 (m, 2H), 7.33-7.31 (m, 2H), 2.46 (s, 3 H). 13C NMR
(126MHz, CDCl3)δ:194.2, 149.4, 144.3, 143.0, 133.3, 130.2, 130.0, 129.1, 123.2, 21.4. MS (ESI)
C14H11NO3: m/z 241.
(4-chlorophenyl)(4-nitrophenyl)methanone (C14): Yellow solid. 1H NMR (500 MHz,
CDCl3)δ:8.35-8.33 (m, 2H), 7.92-7.90 (m, 2H), 7.76-7.74 (m, 2H), 7.51-7.49 (m, 2H). 13C NMR
(126MHz, CDCl3)δ: 193.5, 149.9, 142.4, 140.0, 134.5, 131.4, 130.5, 129.0, 123.6. MS (ESI)
C12H8NClO3: m/z 261.
(3,5-dichlorophenyl)(4-nitrophenyl)methanone (C16): Yellow solid.1H NMR (500 MHz,
CDCl3) δ: 8.39- 8.37 (m, 2H), 7.94-7.92 (m, 2H), 7.65(t, J=2.1 Hz, 3H). 13C NMR (126MHz,
CDCl3)δ: 191.8, 150.0, 141.1, 138.5, 135.5, 132.98, 130.4, 127.9, 123.6. MS (ESI) C13H7NO3Cl2:
m/z 294.
(4-nitrophenyl)(thiophen-3-yl)methanone (C17): White fluffy solid. 1H NMR (500 MHz,
CDCl3): δ:8.35 (d, J=8.8 Hz, 2H), 7.99-7.95 (m, 3H), 7.60 (d, J=5.0 Hz, 1H), 7.45-7.44 (m, 1H). 13C NMR (126MHz, CDCl3) δ:187.6, 149.5, 143.5, 140.1, 134.6, 129.8, 127.9, 126.7, 123.3. MS
(ESI) C11H7NSO3: m/z 233.
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(4-fluorophenyl)(4-nitrophenyl)methanone (C18): Yellowish white solid. 1H NMR (500
MHz, CDCl3)δ: 8.35 (d, J=8.8 Hz, 2H), 7.91 (d, J=8.4 Hz, 2H), 7.85 (dd, J=8.6, 5.5 Hz, 2H),
7.20 (t, J=8.6 Hz, 2H). 13C NMR (126MHz, CDCl3) δ:193.2, 166.9, 149.8, 142.7, 132.8, 132.7,
130.5, 123.6, 116.1. MS (ESI) C13H8NFO3: m/z 245.
Phenyl(p-tolyl)methanone (C19): Yellow oil.1H NMR (200 MHz, CDCl3)δ:7.77-7.71 (m, 4H),
7.67-7.43 (m, 3H), 7.26-7.22 (m, 2H), 2.40 (s, 3H). 13C NMR (50MHz, CDCl3)δ:196.7, 142.7,
137.1, 134.1, 131.4, 129.5, 129.1, 128.2, 127.4, 20.8. MS (ESI) C14H12O: m/z 196.
(naphthalen-1-yl)(p-tolyl)methanone (C21): White fluffy solid.1H NMR (200 MHz, CDCl3)
δ:7.84-7.64 (m, 3H), 7.42 (d, J=8.2 Hz, 2H), 7.41-7.35 (m, 4H), 7.14-7.10 (m, 2H), 2.30 (s, 3H). 13C NMR (50MHz, CDCl3) δ: 197.6, 144.1, 135.6, 130.8, 130.4, 129.0, 128.2, 127.2, 127.0,
126.2, 125.6, 125.6, 124.2, 21.6. MS (ESI) C18H14O: m/z 246.
di(p-tolyl)methanone (C22): White fluffy solid.1H NMR (500 MHz, CDCl3) δ: 7.73 (d, J=8.4
Hz, 4H), 7.30 (d, J=7.6 Hz, 4H), 2.47 (s, 6H). 13C NMR (126MHz, CDCl3)δ: 196.3, 142.9, 135.2,
130.3, 128.9, 21.6. MS (ESI) C15H14O: m/z 210.
(4-chlorophenyl)(p-tolyl)methanone (C23): White solid. 1H NMR (200 MHz, CDCl3)δ: 7.76-
7.67 (m, 13H), 7.47-7.43 (m, 2H), 7.31-7.27 (m, 3H), 2.45 (s, 3H). 13C NMR (50MHz, CDCl3)δ:
195.2, 143.5, 138.5, 134.5, 131.3, 130.1, 129.0, 128.5, 123.6, 21.6. MS (ESI) C14H11OCl: m/z
230.
(4-methyphenyl)(4-cynophenyl)methanone (C24): White solid.1H NMR (500 MHz, CDCl3)
δ:7.85-7.84 (m, 2H), 7.79-7.78 (m, 2H), 7.68-7.67 (m, 2H), 7.31-7.30 (m, 2H), 2.45 (s, 3H). 13C
NMR (126MHz, CDCl3)δ: 194.7, 144.3, 141.6, 133.6, 132.0, 130.2, 130.0, 129.3, 118.0, 115.3,
21.7. MS (ESI) C15H11NO: m/z 221.
(3,5-dichlorophenyl)(p-tolyl)methanone (C25): Yellow liquid. 1H NMR (500 MHz, CDCl3δ:
7.90-7.77 (m, 1H), 7.76 (d, J=7.6 Hz, 2H), 7.57 (d, J=4.6 Hz, 1H), 7.36 (dd, J=4.4, 3.2 Hz, 1H),
7.29 (d, J=7.6 Hz, 2H), 2.43 (s, 3H). 13C NMR (126MHz, CDCl3)δ: 189.6, 143.0, 141.3, 135.8,
133.3, 129.5, 128.9, 128.5, 125.9, 21.5. MS (ESI) C14H10Cl2O: m/z 264.
(thiophen-3-yl)(p-tolyl)methanone (C26): Yellow oil. 1H NMR (500 MHz, CDCl3)δ: 7.69 (d,
J=8.0 Hz, 2H), 7.62 (d, J=1.5 Hz, 2H), 7.54 (s, 1H), 7.30 (d, J=7.6 Hz, 2H), 2.45 (s, 3H). 13C
NMR (126MHz, CDCl3)δ:193.1, 143.9, 140.2, 134.8, 133.3, 129.9, 129.1, 129.0, 127.7, 21.4.
MS (ESI) C12H10OS: m/z 202.
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(4-fluorophenyl)(p-tolyl)methanone (C28): White solid. 1H NMR (500 MHz, CDCl3) δ:7.83
(dd, J= 8.6, 5.5 Hz, 2H), 7.68-7.69 (m, 2H), 7.29-7.28 (m, 2H), 7.15 (t, J=8.6 Hz, 2H), 2.44 (s, 3
H). 13C NMR (126MHz, CDCl3)δ:195.0, 166.2 (C-F coupling), 143.3, 134.7, 134.1, 132.5, 130.1,
129.0, 115.4, 21.6. MS (ESI) C14H101OF: m/z 214.
(4-fluorophenyl)methanone (C29): Colorless liquid.1H NMR (400 MHz, CDCl3) δ7.85-7.89
(m, 2H), 7.74 (d, J=8.0 Hz, 2H), 7.51 (t, J=5.3 Hz, 1H), 7.54 (t, J=5.3 Hz, 2H), 7.18 (t, J=5.3 Hz,
2H). 13C NMR (126MHz, CDCl3) δ: 195.3, 166.7, 137.51, 132.60, 129.92, 128.41, 115.62, 115.4,
112.30. MS (ESI) C13H9FO: m/z 200.
(4-fluorophenyl)(p-tolyl)methanone (C30): White solid. 1H NMR (200 MHz, CDCl3)δ: 7.86-
7.79 (m, 2H), 7.69 (d, J=8.1 Hz, 2H), 7.31-7.27 (m, 2H), 7.20-7.11 (m, 2H), 2.45 (s, 3H). 13C
NMR (50MHz, CDCl3) δ: 195.0, 167.7 (C-F coupling), 143.3, 134.7, 134.0, 132.5, 132.3, 130.1,
129.0, 115.5, 21.6. MS (ESI) C14H11FO: m/z 214.
(4-chlorophenyl)(4-fluorophenyl)methanone (C31): White solid. 1H NMR (500 MHz,
CDCl3)δ: 7.82 (dd, J=8.8, 5.3 Hz, 2H), 7.73-7.71 (m, 2H), 7.48-7.46 (m, 2H), 7.18 (t, J=8.4 Hz,
2H). 13C NMR (126MHz, CDCl3)δ: 193.7, 166.2 (C-F coupling), 138.7, 135.5, 133.2, 132.3,
131.0, 128.4, 115.4. MS (ESI) C13H8FClO: m/z 234.
4-(4-fluorobenzoyl)benzonitrile (C32): White solid. 1H NMR (400 MHz, CDCl3) δ: 8.18-8.21
(m, 4H), 7.23 (t, J=5.3 Hz, 4H). 13C NMR (126MHz, CDCl3)δ: 199.5, 168.0 (C-F coupling),
165.4, 161.2, 133.3, 133.2, 125.0, 116.4, 116.1 MS (ESI) C14H8FNO: m/z 225.
Compounds C31, C152,3, C204:
4. References:
1. Jadhav, S. N.; Kumbhar, A. S.; Rode, C. V.; Salunkhe, R. S. Green Chem. 2016, 18, 1898.
2. Zhou, Q.; Wei, S.; Han, W. J. Org. Chem. 2014, 79, 1454.
3. Wang, X.; Huang, Y.; Xu, Y.; Tang, X.; Wu, W.; Jiang, H. J. Org. Chem. 2017, 82, 2211.
4. Pitts, J. D.; Howell, A.R.; Taboada, R.; Banerjee, I.; Wang, J.; Goodman, S. L.; Campagnola,
P. J. Photochem. Photobiol. 2002, 76, 135.
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5. 1H and 13C NMR spectra for Dissymmetric Ketones
1H NMR spectrum of (4-bromophenyl)(phenyl)methanone (C2):
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13C NMR spectrum of (4-bromophenyl)(phenyl)methanone (C2):
1H NMR spectrum of naphthalene-1-yl(4-nitrophenyl)methanone (C3):
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