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

Bo Chen; Xingang Xie; Jiangping Lu; Qiaoling Wang; Jiyong Zhang; Shouchu Tang; Xuegong She; Xinfu Pan

doi:10.1055/s-2005-923587

LETTER

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

Bo Chen^a, Xingang Xie^a, Jiangping Lu^a, Qiaoling Wang^a, Jiyong Zhang^a, Shouchu Tang^a, 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;

Abstract

All articles of this category

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

Full Text

References

References and Notes

1a Heck RF. Org. React. 1982, 27: 345

1b de Meijere A. Meyer FE. Angew. Chem., Int. Ed. Engl. 1994, 33: 2379

1c Cabri W. Candiani I. Acc. Chem. Res. 1995, 28: 2

1d Beletskaya IP. Cheprakov AV. Chem. Rev. 2000, 100: 3009

1e Amatore C. Jutand A. Acc. Chem. Res. 2000, 33: 314

1f McClure KF. Danishefsky SJ. J. Am. Chem. Soc. 1993, 115: 6094

2 Link J. Org. React. 2002, 60: 157

3a Shibasaki M. Vogl EM. Adv. Synth. Catal. 2004, 346: 1533

3b Dounay AB. Overman LE. Chem. Rev. 2003, 103: 2945

4 Gaudin JM. Tetrahedron Lett. 1991, 32: 6113

5 Bei X. Hagemeyer A. Volpe A. Saxton R. Turner H. Guram AS. J. Org. Chem. 2004, 69: 8626

6

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.

7

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).

8a Iida H. Yuasa Y. Kibayashi C. J. Org. Chem. 1980, 45: 2938

8b Steinhoff BA. Fix SR. Stahl SS. J. Am. Chem. Soc. 2002, 124: 766

8c Schultz MJ. Park CC. Sigman MS. Chem. Commun. 2002, 14: 3034

8d Mueller JA. Sigman MS. J. Am. Chem. Soc. 2003, 125: 7005

9a Ito T. Tanaka T. Iinuma M. Nakaya K. Takahashi Y. Sawa R. Murata J. Darnaedi D. J. Nat. Prod. 2004, 67: 932

9b Ernst-Russell MA. Chai CLL. Wardlaw JH. Elix JA. J. Nat. Prod. 2000, 63: 129

9c Fillion E. Fishlock D. J. Am. Chem. Soc. 2005, 127: 13144

10 Seo EK. Chai H. Constant HL. Santisuk T. Reutrakul V. Beecher CWW. Farnsworth NR. Cordell GA. Pezzuto JM. Kinghorn AD. J. Org. Chem. 1999, 64: 6976

11 Dai JR. Hallock YF. Cardellina JH. Boyd MR. J. Nat. Prod. 1998, 61: 351

12 Samaraweera U. Sotheeswaran S. Sultanbawa MUS. Phytochemistry 1982, 21: 2585

13a Larock RC. Doty MJ. Cacchi S. J. Org. Chem. 1993, 58: 4579

13b Shintani R. Okamoto K. Hayashi T. J. Am. Chem. Soc. 2005, 127: 2872

13c Gevorgyan V. Quan LG. Yamamoto Y. Tetrahedron Lett. 1999, 40: 4089

13d Shintani R. Hayashi T. Org. Lett. 2005, 7: 2071

13e Gagnier SV. Larock RC. J. Am. Chem. Soc. 2003, 125: 4804

13f Rendy R. Zhang Y. McElrea A. Gomez A. Klumpp DA. J. Org. Chem. 2004, 69: 2340

13g Kim DH. Son SU. Chung YK. Org. Lett. 2003, 5: 3151