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Supporting Information Transition metal-free Suzuki type cross-coupling for synthesis of dissymmetric ketones Sanjay Jadhav a , Gajanan Rashinkar a , Rajashri Salunkhe a* , Arjun Kumbhar b * a Department of chemistry, Shivaji University, Kolhapur, 416006, M.S., India. b P, 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. 1 H and 13 C 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. 1 H NMR and 13 C NMR spectra were recorded on a Bruker Avon 200 and 500 MHz spectrometer using CDCl 3 as solvent and 1

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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

1

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),

2

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.

4

(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):

6

13C NMR spectrum of (4-bromophenyl)(phenyl)methanone (C2):

1H NMR spectrum of naphthalene-1-yl(4-nitrophenyl)methanone (C3):

7

13C NMR spectrum of naphthalene-1-yl(4-nitrophenyl)methanone (C3):

8

1H NMR spectrum of phenyl(p-tolyl)methanone (C4):

9

13C NMR spectrum of phenyl(p-tolyl)methanone (C4):

10

1H NMR spectrumof (4-chlorophenyl)(phenyl)methanone (C5):

11

13C NMR spectrum of (4-chlorophenyl)(phenyl)methanone (C5):

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1H NMR spectrum of (4-cynophenyl)(phenyl)methanone (C6):

13

13C NMR spectrum of (4-cynophenyl)(phenyl)methanone (C6):

14

1H NMR spectrum of (3,5-dichlorophenyl)(phenyl)methanone (C7):

15

1C NMR spectrum of (3,5-dichlorophenyl)(phenyl)methanone (C7):

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1H NMR spectrum of phenyl(thiophen-3-yl)methanone (C8):

17

13C NMR spectrum of phenyl(thiophen-3-yl)methanone (C8):

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1H NMR spectrum of (4-fluorophenyl)(phenyl)methanone (C9):

19

13C NMR spectrum of (4-fluorophenyl)(phenyl)methanone (C9):

20

1H NMR spectrum of (4-nitrophenyl)(phenyl)methanone (C10):

21

13C NMR spectrum of (4-nitrophenyl)(phenyl)methanone (C10):

22

1H NMR spectrum of (4-ethylphenyl)(4-nitrophenyl)methanone (C11):

23

13C NMR spectrum of (4-ethylphenyl)(4-nitrophenyl)methanone (C11):

24

1H NMR spectrum of naphthalene-1-yl(4-nitrophenyl)methanone (C12):

25

13C NMR spectrum of naphthalene-1-yl(4-nitrophenyl)methanone (C12):

26

1H NMR spectrum of (4-nitrophenyl)(p-tolyl)methanone (C13):

27

13C NMR spectrum of (4-nitrophenyl)(p-tolyl)methanone (C13):

28

1H NMR spectrum of (4-chlorophenyl)(4-nitrophenyl)methanone (C14):

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13C NMR spectrum of (4-chlorophenyl)(4-nitrophenyl)methanone (C14):

30

1H NMR spectrum of (3,5-dichlorophenyl)(4-nitrophenyl)methanone (C16):

31

13C NMR spectrum of (3,5-dichlorophenyl)(4-nitrophenyl)methanone (C16):

32

1H NMR spectrum of (4-nitrophenyl)(thiophen-3-yl)methanone (C17):

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13C NMR spectrum of (4-nitrophenyl)(thiophen-3-yl)methanone (C17):

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1H NMR spectrum of (4-fluorophenyl)(4-nitrophenyl)methanone (C18):

35

13C NMR spectrum of (4-fluorophenyl)(4-nitrophenyl)methanone (C18):

36

1H NMR spectrum of Phenyl(p-tolyl)methanone (C19):

37

13C NMR spectrum of Phenyl(p-tolyl)methanone (C19):

38

1H NMR spectrum of (naphthalen-1-yl)(p-tolyl)methanone (C21):

39

13C NMR spectrum of (naphthalen-1-yl)(p-tolyl)methanone (C21):

40

1H NMR spectrum of di(p-tolyl)methanone (C22):

41

13C NMR spectrum of di(p-tolyl)methanone (C22):

42

1H NMR spectrum of (4-chlorophenyl)(p-tolyl)methanone (C23):

43

13C NMR spectrum of (4-chlorophenyl)(p-tolyl)methanone (C23):

44

1H NMR spectrum (4-methyphenyl)(4-cynophenyl)methanone (C24):

45

13C NMR spectrum (4-methyphenyl)(4-cynophenyl)methanone (C24):

46

1H NMR spectrum of (3,5-dichlorophenyl)(p-tolyl)methanone (C25):

47

13C NMR spectrum of (3,5-dichlorophenyl)(p-tolyl)methanone (C25):

48

1H NMR spectrum of (thiophen-3-yl)(p-tolyl)methanone (C26):

49

13C NMR spectrum of (thiophen-3-yl)(p-tolyl)methanone (C26):

50

1H NMR spectrum of (4-fluorophenyl)(p-tolyl)methanone (C28):

51

13C NMR spectrum of (4-fluorophenyl)(p-tolyl)methanone (C28):

52

1H NMR spectrum of (4-fluorophenyl)methanone (C29):

53

13C NMR spectrum of (4-fluorophenyl)methanone (C29):

54

1H NMR spectrum of (4-fluorophenyl)(p-tolyl)methanone (C30):

55

13C NMR spectrum of (4-fluorophenyl)(p-tolyl)methanone (C30):

56

1H NMR spectrum of (4-chlorophenyl)(4-fluorophenyl)methanone (C31):

57

13C NMR spectrum of (4-chlorophenyl)(4-fluorophenyl)methanone (C31):

58

1H NMR spectrum of 4-(4-fluorobenzoyl)benzonitrile (C32):

59

13C NMR spectrum of 4-(4-fluorobenzoyl)benzonitrile (C32):

60

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