Subscribe to RSS
DOI: 10.1055/s-2008-1042917
A Novel InCl3/SiO2-Catalyzed Hydroarylation of Arenes with Styrenes under Solvent-Free Conditions
Publication History
Publication Date:
17 March 2008 (online)
![](https://www.thieme-connect.de/media/synlett/200807/lookinside/thumbnails/10.1055-s-2008-1042917-1.jpg)
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
-
1a
Evans DA.Katz JL.West TR. Tetrahedron Lett. 1998, 39: 2937 -
1b
Paluchi M.Buchwald SL. J. Am. Chem. Soc. 1997, 45: 11108 -
1c
Kawatsura M.Hartwig JF. J. Am. Chem. Soc. 1999, 121: 1473 -
1d
Klapars A.Antilla JC.Huang XH.Buchwald SL. J. Am. Chem. Soc. 2001, 123: 7727 -
1e
Daugulis O.Zaitsev VG. Angew. Chem. Int. Ed. 2005, 26: 4046 -
1f
Bressy C.Alberico D.Lautens M. J. Am. Chem. Soc. 2005, 127: 13148 -
1g
Campeau LC.Fagnou K. Chem. Commun. 2006, 12: 1253 -
1h
Giri T.Maugel N.Li JJ.Wang DH.Breazzano SP.Saunders LB.Yu JQ. J. Am. Chem. Soc. 2007, 129: 3510 -
1i
Ellman JA. Science 2007, 316: 1131 -
1j
Stuart DR.Fagnou K. Science 2007, 316: 1172 -
1k
Proch S.Kempe R. Angew. Chem. Int. Ed. 2007, 46: 3135 -
1l
Gois PMR.Trindade AF.Verros LF.André V.Duarte MT.Afonso CAM.Caddick S.Cloke FGN. Angew. Chem. Int. Ed. 2007, 46: 5750 -
2a
Nordberg MG.Kolmodin K.Aquist J.Queener SF.Hallberg A. J. Med. Chem. 2001, 44: 2391 -
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 -
3a
Mertins K.Iovel I.Kischel J.Zapf A.Beller M. Angew. Chem. Int. Ed. 2005, 44: 238 -
3b
Iovel I.Mertins K.Kischel J.Zapf A.Beller M. Angew. Chem. Int. Ed. 2005, 44: 3913 -
3c
Mertins K.Iovel I.Kischel J.Zapf A.Beller M. Adv. Synth. Catal. 2006, 348: 691 -
3d
Rueping M.Nachtsheim BJ.Ieawsuwan W. Adv. Synth. Catal. 2006, 348: 1033 -
3e
Kischel J.Jovel I.Zapf A.Beller M. Org. Lett. 2006, 8: 19 -
3f
Rueping M.Nachtsheim BJ.Scheidt T. Org. Lett. 2006, 8: 3717 -
3g
Tsuchimoto T.Tobita K.Hiyama T.Fukuzawa S. J. Org. Chem. 1997, 62: 6997 -
3h
Sun H.-B.Li B.Hua R.Yin YW. Eur. J. Org. Chem. 2006, 4231 - Selected recent examples for this reaction:
-
4a
Deshpande AB.Bajpai AR.Samant SD. Appl. Catal. 2001, 209: 229 -
4b
Hu X.Chuah GK.Jaenicke S. Appl. Catal. 2001, 217: 1 -
4c
Choudhary VR.Jana SK. J. Catal. 2001, 201: 225 -
4d
Choudhary VR.Jana SK.Narkhede VS. Appl. Catal. 2002, 235: 207 -
4e
Shrigadi NB.Shinde AB.Samant SD. Appl. Catal. 2003, 252: 23 -
4f
Bachari K.Millet JMM.Benaichouba B.Cherifi O.Figueras F. J. Catal. 2004, 221: 55 -
4g
Salavati-Niasari M.Hasanalian J.Najafian H. J. Mol. Catal. A: Chem. 2004, 209: 209 -
4h
Choudhary VR.Jha R.Choudhari PA. J. Chem. Sci. 2005, 117: 635 -
4i
Choudhary VR.Jha R.Narkhede VS. J. Mol. Catal. A: Chem. 2005, 239: 76 -
6a
Hui AL.Xu XL.Zha ZG.Zhou CL.Wang ZY. ARKIVOC 2004, (ix): 52 -
6b
Zhou CL.Jiang JY.Zhou YQ.Xie Z.Miao Q.Wang ZY. Lett. Org. Chem. 2005, 2: 61 -
7a
Screttas GC.Micha-Screttas M. J. Org. Chem. 1978, 43: 1064 -
7b
Kanagasabapathy S.Sudalai A.Benicewicz BC. Tetrahedron Lett. 2001, 42: 3791
References and Notes
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.
8The 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.
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.