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Synlett 2006(2): 259-262  
DOI: 10.1055/s-2005-923587
LETTER
© Georg Thieme Verlag Stuttgart · New York

A Facile Approach to the Construction of 1H-Inden-1-one

Bo Chena, Xingang Xiea, Jiangping Lua, Qiaoling Wanga, Jiyong Zhanga, Shouchu Tanga, Xuegong She*a,b, Xinfu Pan*a
a State Key Laboratory of Applied Organic Chemistry, Department of Chemistry, Lanzhou University, Lanzhou, 730000, P. R. of China
b State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Science, Lanzhou, 730000, P. R. of China
Fax: +86(931)8912582; e-Mail: shexg@lzu.edu.cn panxf@lzu.edu.cn;
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Publication History

Received 8 October 2005
Publication Date:
23 December 2005 (online)

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Abstract

The one-pot synthesis of 1H-inden-1-one from 1-(2-bromoaryl)prop-2-en-1-ol was described. The reaction involved a sequential intramolecular Heck reaction followed by an aerial oxidation of allylic alcohol.

Key words

1H-inden-1-one - Heck reaction - aerial oxidation - Pd-catalyzed - one-pot

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General Reaction Procedure.
Compound 3 (1 mmol) was dissolved in DMF (5 mL); K2CO3 (200 mol%), Pd(OAc)2 (5 mol%) and PPh3 (15 mol%) were added in turn. The reaction was heated to 80 °C and stirred for 24 h. The reaction mixture was extracted with Et2O (3 × 20 mL), washed with brine, dried with Na2SO4, filtered and evaporated under reduced pressure. The product 4 was purified by column chromatography on silica gel using PE-EtOAc as eluent.

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Spectroscopic Data.
4,6-Dimethoxy-3-(3,5-dimethoxyphenyl)-2-(4-methoxy-phenyl)-1 H -inden-1-one ( 2).
1H NMR (300 MHz, CDCl3): δ = 7.10 (d, J = 8.7 Hz, 2 H), 6.85 (s, 1 H), 6.73 (d, J = 8.7 Hz, 2 H), 6.49 (d, J = 2.1 Hz, 2 H), 6.43 (s, 2 H), 3.85 (s, 3 H), 3.76 (s, 3 H), 3.69 (s, 6 H), 3.60 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 196.6, 162.4, 160.1, 158.6, 156.5, 154.6, 136.9, 134.0, 130.9, 130.5, 123.5, 114.2, 108.0, 103.9, 102.6, 100.9, 55.8, 55.6, 55.3, 55.1. ESI-HRMS: m/z calcd for C26H25O6 [M + H]+: 433.1646; found: 433.1648.
2,3-Diphenyl-1 H -inden-1-one ( 4a).
1H NMR (300 MHz, CDCl3): δ = 7.58 (d, J = 6.0 Hz, 1 H), 7.40-7.42 (m, 4 H), 7.35-7.39 (m, 2 H), 7.24-7.26 (m, 6 H), 7.14 (d, J = 6.0 Hz, 1 H). 13C NMR (75 MHz, CDCl3): δ = 196.5, 155.3, 145.2, 133.4, 132.6, 130.7, 129.9, 129.6, 129.3, 128.9, 128.7, 128.5, 128.0, 127.7, 126.3, 122.9, 121.2. ESI-HRMS: m/z calcd for C21H15O [M + H]+: 283.1117; found: 283.1114.
3-(4-Methoxyphenyl)-1 H -inden-1-one ( 4b).
1H NMR (300 MHz, CDCl3): δ = 8.00 (d, J = 7.2 Hz, 2 H), 7.76 (d, J = 15.6 Hz, 1 H), 7.47-7.61 (m, 3 H), 7.39 (d, J = 15.6 Hz, 1 H), 6.92 (d, J = 7.2 Hz, 2 H). 13C NMR (75 MHz, CDCl3): δ = 190.6, 161.6, 144.7, 138.4, 132.5, 130.2, 128.5, 128.3, 127.5, 119.7, 114.3, 55.3. ESI-HRMS: m/z calcd for C16H13O [M + H]+: 221.0966; found: 221.0963.
2-(4-Methoxyphenyl)-3-phenyl-1 H -inden-1-one ( 4c).
1H NMR (300 MHz, CDCl3): δ = 7.55 (d, J = 6.3 Hz, 1 H), 7.41-7.43 (m, 5 H), 7.28-7.41 (m, 3 H), 7.20 (d, J = 6.3 Hz, 2 H), 7.09 (d, J = 7.2 Hz, 1 H), 6.78 (d, J = 6.3 Hz, 2 H). 13C NMR (75 MHz, CDCl3): δ = 197.0, 159.1, 153.7, 145.5, 133.4, 132.9, 131.8, 131.2, 130.6, 129.1, 128.7, 128.6, 128.4, 123.0, 122.8, 120.9, 113.6, 55.1. ESI-HRMS: m/z calcd for C22H17O2 [M + H]+: 313.1223; found: 313.1225.
3-(4-Methoxyphenyl)-2-phenyl-1 H -inden-1-one ( 4d).
1H NMR (300 MHz, CDCl3): δ = 7.56 (d, J = 7.2 Hz, 1 H), 7.19-7.38 (m, 11 H), 6.91 (d, J = 8.7 Hz, 2 H), 3.85 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 196.4, 160.4, 155.2, 145.1, 133.2, 131.6, 131.0, 130.2, 129.9, 128.8, 128.1, 127.5, 126.1, 124.7, 122.7, 121.2, 114.1, 55.2. ESI-HRMS: m/z calcd for C22H17O2 [M + H]+: 313.1223; found: 313.1223.
3-(4-Nitrophenyl)-2-phenyl-1 H -inden-1-one ( 4e).
1H NMR (300 MHz, CDCl3): δ = 8.26 (d, J = 8.1 Hz, 2 H), 7.60 (d, J = 7.2 Hz, 1 H), 7.55 (d, J = 8.1 Hz, 2 H), 7.19-7.44 (m, 7 H), 7.07 (d, J = 6.9 Hz, 1 H). 13C NMR (75 MHz, CDCl3): δ = 195.5, 152.2, 147.9, 144.2, 139.5, 134.0, 133.8, 130.1, 129.8, 129.5, 129.4, 128.3, 124.1, 123.5, 120.8. FAB-MS: m/z = 328.1, 307.2.
4,6-Dimethoxy-3-phenyl-1 H -inden-1-one ( 4f).
1H NMR (300 MHz, CDCl3): δ = 7.60 (d, J = 6.9 Hz, 2 H), 7.42-7.48 (m, 3 H), 6.81 (d, J = 1.8 Hz, 1 H), 6.44 (d, J = 1.8 Hz, 1 H), 5.69 (s, 1 H), 3.85 (s, 3 H), 3.68 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 196.5, 166.3, 163.1, 136.1, 134.9, 130.9, 129.7, 127.8, 127.6, 122.1, 107.2, 103.2, 102.6, 55.8, 54.3. ESI-HRMS: m/z calcd for C17H14O3Na [M + Na]+: 289.0835; found: 289.0832.
2-(4-Methoxyphenyl)-3-(4-nitrophenyl)-1 H -inden-1-one ( 4g).
1H NMR (300 MHz, CDCl3): δ = 8.27 (d, J = 8.7 Hz, 2 H), 7.56-7.60 (m, 3 H), 7.36-7.41 (m, 1 H), 7.25-7.32 (m, 1 H), 7.15 (d, J = 9.0 Hz, 2 H), 7.02 (d, J = 6.9 Hz, 1 H), 6.79 (d, J = 9.0 Hz, 2 H), 3.79 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 196.0, 159.7, 150.6, 147.8, 144.6, 140.0, 133.7, 133.5, 131.2, 130.1, 129.6, 129.0, 124.1, 123.4, 121.9, 120.4, 113.9, 55.2. IR (KBr): 1710, 1602, 1512, 1456, 1343, 1292, 1250, 1177 cm-1. FAB-MS: m/z = 356.9, 341.9.
2,3-Dihydro-4,6-dimethoxy-3-(4-methoxyphenyl)-2-propylideneinden-1-one ( 4h). 1H NMR (300 MHz, CDCl3): δ = 7.03 (d, J = 11.7 Hz, 2 H), 6.92 (s, 1 H), 6.73-6.83 (m, 3 H), 6.56 (s, 1 H), 4.92 (s, 1 H), 3.88 (s, 3 H), 3.79 (s, 3 H), 3.64 (s, 3 H), 1.94-2.15 (m, 2 H), 0.88 (t, J = 7.5, 7.5 Hz, 3 H). 13C NMR (75 MHz, CDCl3): δ = 193.9, 161.3, 157.8, 157.5, 141.5, 140.4, 139.5, 136.1, 134.1, 129.1, 113.3, 106.1, 96.4, 55.7, 55.5, 55.0, 44.1, 22.4, 12.3. MS (EI): m/z (%) = 338 (14) [M+], 245 (43), 166 (72), 138 (100).