A Novel InCl3/SiO2-Catalyzed Hydroarylation of Arenes with Styrenes under Solvent-Free Conditions

Gaojun Sun; Huayin Sun; Zhiyong Wang; Ming-Ming Zhou

doi:10.1055/s-2008-1042917

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Synlett 2008(7): 1096-1100
DOI: 10.1055/s-2008-1042917

LETTER

A Novel InCl₃/SiO₂-Catalyzed Hydroarylation of Arenes with Styrenes under Solvent-Free Conditions

Gaojun Sun^a, Huayin Sun^a, Zhiyong Wang*^a, Ming-Ming Zhou*^b
^a Hefei National Laboratory for Physical Science at Microscale and Department of Chemistry, University of Science and Technology of China, Hefei, Anhui, 230026, P. R. of China
Fax: +86(551)3603185; e-Mail: zwang3@ustc.edu.cn;
^b Department of Physiology and Biophysics, Mount Sinai School of Medicine, New York University, One Gustave L. Levy Place, New York, NY 10029-6574, USA

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Publikationsverlauf

Received 24 December 2007
Publikationsdatum:
17. März 2008 (online)

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Abstract

A novel InCl₃/SiO₂-catalyzed hydroarylation of various styrenes with arenes has been developed. The reaction can be carried out under solvent-free conditions to afford a series of 1,1-diarylalkanes in high yields and with good regioselectivities. The catalyst can be reused six times without obvious loss of catalytic activity.

Key words

hydroarylation - 1,1-diarylalkane - heterogeneous catalyst - regioselectivity - solvent-free

References and Notes

1a Evans DA. Katz JL. West TR. Tetrahedron Lett. 1998, 39: 2937

Crossref Google Scholar
1b Paluchi M. Buchwald SL. J. Am. Chem. Soc. 1997, 45: 11108

Crossref Google Scholar
1c Kawatsura M. Hartwig JF. J. Am. Chem. Soc. 1999, 121: 1473

Crossref Google Scholar
1d Klapars A. Antilla JC. Huang XH. Buchwald SL. J. Am. Chem. Soc. 2001, 123: 7727

Crossref Google Scholar
1e Daugulis O. Zaitsev VG. Angew. Chem. Int. Ed. 2005, 26: 4046

Crossref Google Scholar
1f Bressy C. Alberico D. Lautens M. J. Am. Chem. Soc. 2005, 127: 13148

Crossref Google Scholar
1g Campeau LC. Fagnou K. Chem. Commun. 2006, 12: 1253

Crossref Google Scholar
1h Giri T. Maugel N. Li JJ. Wang DH. Breazzano SP. Saunders LB. Yu JQ. J. Am. Chem. Soc. 2007, 129: 3510

Crossref Google Scholar
1i Ellman JA. Science 2007, 316: 1131

Crossref Google Scholar
1j Stuart DR. Fagnou K. Science 2007, 316: 1172

Crossref Google Scholar
1k Proch S. Kempe R. Angew. Chem. Int. Ed. 2007, 46: 3135

Crossref Google Scholar
1l Gois PMR. Trindade AF. Verros LF. André V. Duarte MT. Afonso CAM. Caddick S. Cloke FGN. Angew. Chem. Int. Ed. 2007, 46: 5750

Crossref Google Scholar
2a Nordberg MG. Kolmodin K. Aquist J. Queener SF. Hallberg A. J. Med. Chem. 2001, 44: 2391

Crossref Google Scholar
2b Rose C. Vtoraya O. Pluzanska A. Davidson N. Gershanovich M. Thomas R. Johnson S. Caicedo JJ. Gervasio H. Manikhas G. Ayed FB. Radoux SB. Ross HAC. Lang R. Eur. J. Cancer 2003, 39: 2318

Crossref Google Scholar
3a Mertins K. Iovel I. Kischel J. Zapf A. Beller M. Angew. Chem. Int. Ed. 2005, 44: 238

Crossref Google Scholar
3b Iovel I. Mertins K. Kischel J. Zapf A. Beller M. Angew. Chem. Int. Ed. 2005, 44: 3913

Crossref Google Scholar
3c Mertins K. Iovel I. Kischel J. Zapf A. Beller M. Adv. Synth. Catal. 2006, 348: 691

Crossref Google Scholar
3d Rueping M. Nachtsheim BJ. Ieawsuwan W. Adv. Synth. Catal. 2006, 348: 1033

Crossref Google Scholar
3e Kischel J. Jovel I. Zapf A. Beller M. Org. Lett. 2006, 8: 19

Crossref Google Scholar
3f Rueping M. Nachtsheim BJ. Scheidt T. Org. Lett. 2006, 8: 3717

Crossref Google Scholar
3g Tsuchimoto T. Tobita K. Hiyama T. Fukuzawa S. J. Org. Chem. 1997, 62: 6997

Crossref Google Scholar
3h Sun H.-B. Li B. Hua R. Yin YW. Eur. J. Org. Chem. 2006, 4231

Crossref Google Scholar
Selected recent examples for this reaction:
4a Deshpande AB. Bajpai AR. Samant SD. Appl. Catal. 2001, 209: 229

Crossref Google Scholar
4b Hu X. Chuah GK. Jaenicke S. Appl. Catal. 2001, 217: 1

Crossref Google Scholar
4c Choudhary VR. Jana SK. J. Catal. 2001, 201: 225

Crossref Google Scholar
4d Choudhary VR. Jana SK. Narkhede VS. Appl. Catal. 2002, 235: 207

Crossref Google Scholar
4e Shrigadi NB. Shinde AB. Samant SD. Appl. Catal. 2003, 252: 23

Crossref Google Scholar
4f Bachari K. Millet JMM. Benaichouba B. Cherifi O. Figueras F. J. Catal. 2004, 221: 55

Crossref Google Scholar
4g Salavati-Niasari M. Hasanalian J. Najafian H. J. Mol. Catal. A: Chem. 2004, 209: 209

Crossref Google Scholar
4h Choudhary VR. Jha R. Choudhari PA. J. Chem. Sci. 2005, 117: 635

Crossref Google Scholar
4i Choudhary VR. Jha R. Narkhede VS. J. Mol. Catal. A: Chem. 2005, 239: 76

Crossref Google Scholar
6a Hui AL. Xu XL. Zha ZG. Zhou CL. Wang ZY. ARKIVOC 2004, (ix): 52

Crossref Google Scholar
6b Zhou CL. Jiang JY. Zhou YQ. Xie Z. Miao Q. Wang ZY. Lett. Org. Chem. 2005, 2: 61

Crossref Google Scholar
7a Screttas GC. Micha-Screttas M. J. Org. Chem. 1978, 43: 1064

Crossref Google Scholar
7b Kanagasabapathy S. Sudalai A. Benicewicz BC. Tetrahedron Lett. 2001, 42: 3791

Crossref Google Scholar

5

The catalyst (InCl₃/SiO₂) was prepared by adding SiO₂ (500 mg, 200-300 mesh) to a stirred solution of InCl₃×4H₂O (1 mmol) in CHCl₃ (10 mL) followed by evaporation of the solvent in vacuo.

8

The catalyst can be recovered by washing the mixture with petroleum ether, followed by the removal of the solvent.

9

Typical Procedure for the FC-Arylation of Styrenes
In a typical experiment, InCl₃/SiO₂ (0.025 mmol, 5 mol%), styrene (0.5 mmol, 1 equiv), and anisole (0.55 mmol, 1.1 equiv) were mixed. The solution was heated at 80 °C for 2 h, cooled down, and gently evaporated under vacuo. The resulting crude mixture was purified by column chromatography on SiO₂ (gradient hexane to hexane-
EtOAc = 100:1) to afford 97 mg (91%) of a colorless oily product.

10

Spectroscopic Data for Products 1-Methyl-4-(1-phenylethyl)benzene (1a): ¹H NMR (300 MHz, CDCl₃): δ = 7.36-7.10 (m, 9 H), 4.11 (q, J = 7.2 Hz, 1 H), 2.30 (s, 4 H), 1.60 (d, J = 7.5 Hz, 3 H). 1,4-Dimethyl-2-(1-phenylethyl)benzene (1b): ¹H NMR (300 MHz, CDCl₃): δ = 7.23-6.95 (m, 9 H), 4.29 (q, J = 6.9 Hz, 1 H), 2.32 (s, 3 H), 2.18 (s, 2 H), 1.60 (d, J = 7.2 Hz, 3 H). 1,2-Dimethyl-4-(1-phenylethyl)benzene (1c): ¹H NMR (300 MHz, CDCl₃): δ = 7.20-6.93 (m, 8 H), 4.07 (q, J = 7.2 Hz, 1 H), 2.20 (s, 6 H), 1.60 (d, J = 7.2 Hz, 3 H). 2,4-Dimethyl-1-(1-phenylethyl)benzene (1d): ¹H NMR (300 MHz, CDCl₃): δ = 7.27-6.95 (m, 8 H), 4.28 (q, J = 7.2 Hz, 1 H), 2.29 (s, 3 H), 2.19 (s, 3 H), 1.59 (d, J = 7.5 Hz, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 146.6, 141.1, 136.0, 135.6, 131.4, 128.4, 127.8, 126.8, 125.9, 40.8, 22.3, 21.0, 19.8. IR (film): ν = 3024, 2966, 2926, 2872, 1601, 1493, 1451, 1374, 1307, 1192, 1028, 822, 762, 747, 700 cm^-1. HRMS: m/z calcd for C₁₆H₁₈: 210.3142; found: 210.3133. 1,2,3,4-Tetrahydro-6-(1-phenylethyl)naphthalene (1e): ¹H NMR (300 MHz, CDCl₃): δ = 7.24-6.92 (m, 8 H), 4.08 (q, J = 7.2 Hz, 1 H), 2.72 (s, 4 H), 1.76 (s, 4 H), 1.61 (d, J = 7.5 Hz, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 146.8, 143.6, 137.1, 134.9, 129.2, 128.4, 128.3, 127.7, 126.0, 124.9, 44.6, 29.6, 29.1, 23.4, 22.1. IR (film): 3025, 2928, 2857, 1735, 1601, 1496, 1451, 1373, 1284, 1028, 910, 829, 766, 699 cm^-1. HRMS: m/z calcd for C₂₂H₂₈: 292.2191; found: 292.2181. 1-Methoxy-4-(1-phenylethyl)benzene (1f): ¹H NMR (300 MHz, CDCl₃): δ = 7.30-7.12 (m, 7 H), 6.82 (d, J = 8.6 Hz, 2 H), 4.10 (q, J = 6.9 Hz, 1 H), 3.77 (s, 3 H), 1.76, (d, J = 7.2 Hz, 3 H). 1,2-Dimethoxy-4-(1-phenylethyl)benzene (1g): ¹H NMR (300 MHz, CDCl₃): δ = 7.28-7.15 (m, 5 H), 6.79 (s, 2 H), 6.72 (s, 1 H), 4.09 (q, J = 7.5 Hz, 1 H), 3.85 (s, 3 H), 3.82 (s, 3 H), 1.62 (d, J = 7.2 Hz, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 148.9, 146.7, 139.1, 128.4, 128.3, 127.65, 127.55, 127.5, 126.1, 119.4, 111.3, 111.2, 55.94, 55.87, 44.4, 22.1. IR (film): 3440, 3059, 3025, 2964, 2932, 2872, 2833, 1727, 1602, 1591, 1516, 1451, 1416, 1252, 1236, 1143, 1029, 908, 855, 810, 764, 701 cm^-1. HRMS: m/z calcd for C₁₆H₁₈O₂: 242.1307; found: 242.1295.
1,5-Dimethoxy-2,4-bis(1-phenylethyl)benzene (1h): ¹H NMR (300 MHz, CDCl₃): δ = 7.24-7.11 (m, 10 H), 7.00 (s, 1 H), 6.39 (s, 1 H), 4.45 (q, J = 7.2 Hz, 1 H), 3.73 (s, 1 H), 1.53 (d, J = 7.2 Hz, 3 H), 1.51 (d, J = 7.2 Hz, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 156.0, 147.1, 132.2, 128.2, 128.1, 127.68, 127.66, 127.0, 126.8, 126.5, 125.6, 96.0, 55.9, 37.4, 21.3. IR (KBr): 3447, 3024, 2961, 2920, 1610, 1583, 1505, 1491, 1464, 1448, 1293, 1205, 1120, 1033, 839, 821, 757, 744, 697 cm^-1. HRMS: m/z calcd for C₂₄H₂₆O₂: 346.1933; found: 346.1922. 2-(1-Phenylethyl)phenol (1i): ¹H NMR (300 MHz, CDCl₃): δ = 7.32-6.73 (s, 8 H), 4.69 (s, 1 H), 4.37 (q, J = 7.2 Hz, 1 H), 1.63 (d, J = 7.2 Hz, 3 H). 4-Methyl-2-(1-phenylethyl)phenol (1j): ¹H NMR (300 MHz, CDCl₃): δ = 7.26-7.19 (m, 5 H), 7.03 (s, 3 H), 6.91 (d, J = 7.8 Hz, 1 H), 6.65 (d, J = 8.1 Hz, 1 H), 4.33 (q, J = 7.2 Hz, 1 H), 2.29 (s, 3 H), 1.62 (d, J = 7.2 Hz, 3 H). Phenethyl(p-tolyl)sulfane (1k): ¹H NMR (300 MHz, CDCl₃): δ = 7.29-7.10 (m, 9 H), 3.13 (t, J = 7.5 Hz, 2 H), 2.90 (t, J = 7.8 Hz, 2 H), 2.33 (s, 3 H). 2-(1-Phenylethyl)thiophene (1l): ¹H NMR (300 MHz, CDCl₃): δ = 7.25-7.13 (m, 7 H), 6.57 (d, J = 4.8 Hz, 1 H), 4.22 (q, J = 7.2 Hz, 1 H), 1.63 (d, J = 7.2 Hz, 3 H). 1-Methoxy-4-(1-p-tolylethyl)benzene (2b): ¹H NMR (300 MHz, CDCl₃): δ = 7.31-6.97 (m, 6 H), 6.94-6.76 (m, 2 H), 4.06 (q, J = 7.2 Hz, 1 H), 3.76 (s, 3 H), 2.26 (s, 3 H), 1.59 (d, J = 7.2 Hz, 3 H). 1-Methoxy-4-(2-phenylpropan-2-yl)benzene (2c): ¹H NMR (300 MHz, CDCl₃): δ = 7.26-7.24 (m, 4 H), 7.16-7.13 (m, 3 H), 6.82-6.79 (m, 2 H), 3.78 (s, 3 H), 1.66 (s, 6 H). 1-[1-(4-Methoxyphenyl)-1-phenylethyl]benzene (2d): ¹H NMR (300 MHz, CDCl₃): δ = 7.28-7.19 (m, 6 H), 7.11-7.10 (m, 3 H), 7.02-6.99 (m, 2 H), 6.79-6.78 (m, 2 H), 3.79 (s, 3 H), 2.16 (s, 6 H). 1-[1-(2-Chlorophenyl)ethyl]-4-methoxybenzene (2e): ¹H NMR (300 MHz, CDCl₃): δ = 7.33 (d, J = 8.4 Hz, 1 H), 7.20-7.11 (m, 5 H), 6.82 (d, J = 8.4 Hz, 2 H), 4.60 (q, J = 7.2 Hz, 1 H), 3.77 (s, 3 H), 1.59 (d, J = 6.6 Hz, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 158.1, 144.2, 137.2, 133.9, 128.8, 128.6, 127.3, 127.0, 113.9, 55.3, 40.2, 21.4. IR (KBr): 3435, 3056, 3008, 2959, 2925, 2852, 1628, 1599, 1468, 1431, 1339, 1289, 1243, 1122, 1066, 1049, 1030, 931, 853, 787, 755, 729, 681 cm^-1. HRMS: m/z calcd for C₁₅H₁₅ClO: 246.0811; found: 246.0800. 1-[1-(4-Chlorophenyl)ethyl]-4-methoxybenzene (2f): ¹H NMR (300 MHz, CDCl₃): δ = 7.23 (d, J = 8.1 Hz, 2 H), 7.14-7.08 (m, 4 H), 6.82 (d, J = 8.7 Hz, 2 H), 4.07 (q, J = 7.2 Hz, 1 H), 3.77 (s, 3 H), 1.58 (d, J = 7.2 Hz, 3 H). 1-[1-(4-Fluorophenyl)ethyl]-4-methoxybenzene (2g): ¹H NMR (300 MHz, CDCl₃): δ = 7.18-7.10 (m, 4 H), 6.99-6.91 (m, 2 H), 6.83-6.82 (m, 2 H), 4.10 (q, J = 7.2 Hz, 1 H), 3.79 (s, 3 H), 1.60 (d, J = 7.2 Hz, 3 H). 1-[1-(2,6-Dichlorophenyl)ethyl]-4-methoxybenzene (2h): ¹H NMR (400 MHz, CDCl₃): δ = 7.48 (d, J = 7.5 Hz, 1 H), 7.20 (d, J = 7.6 Hz, 3 H), 7.02-6.97 (m, 2 H), 6.77 (d, J = 8.1 Hz, 1 H), 5.11 (q, J = 7.3 Hz, 1 H), 1.70 (d, J = 7.4 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 157.6, 141.2, 135.5, 131.2, 129.3, 129.0, 127.4, 127.1, 119.8, 110.5, 55.3, 36.3, 15.7. IR (KBr): 3433, 3070, 2996, 2962, 2920, 2854, 1590, 1557, 1488, 1459, 1430, 1244, 1124, 1124, 1030, 779, 755, 726 cm^-1. HRMS: m/z calcd for C₁₅H₁₄Cl₂O: 280.0422; found: 280.00410. 4-[1-(4-Methoxyphenyl)ethyl]benzonitrile (2i): ¹H NMR (300 MHz, CDCl₃): δ = 7.57-7.54 (m, 2 H), 7.31-7.26 (m, 2 H), 7.09 (d, J = 5.7 Hz, 2 H), 6.84 (dd, J ₁ = 2.1 Hz, J ₂ = 4.5 Hz, 2 H), 4.14 (q, J = 7.2 Hz, 1 H), 3.78 (s, 3 H), 1.61 (d, J = 7.2 Hz, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 158.3, 152.5, 136.9, 132.3, 128.6, 128.4, 119.2, 114.1, 109.9, 55.4, 44.2, 21.7. IR (film): 3401, 3034, 2966, 2959, 2929, 2840, 2227, 1608, 1509, 1459, 1299, 1247, 1178, 1117, 835, 752 cm^-1. HRMS: m/z calcd for C₁₆H₁₅NO: 237.1154; found: 237.1138. 1-Methoxy-3-(1,2-diphenylethyl)benzene (2j): ¹H NMR (400 MHz, CDCl₃): δ = 7.24-7.09 (m, 10 H), 7.00-6.98 (m, 2 H), 6.77 (d, J = 8.8 Hz, 2 H), 4.18 (t, J = 7.8 Hz, 1 H), 3.74 (s, 3 H), 3.3 (d, J = 7.8 Hz, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 158.0, 145.0, 140.5, 136.7, 129.2, 128.4, 128.1, 128.0, 126.2, 125.9, 55.3, 52.3, 42.4. IR (KBr): 3444, 3025, 2933, 1610, 1583, 1509, 1453, 1246, 1179, 1035, 833, 740, 697 cm^-1. HRMS: m/z calcd for C₂₁H₂₀O: 288.1514; found: 288.1511.