DMAP-Catalyzed Benzannulation of Ethyl Propiolate with β-Dicarbonyl Moieties

Qing-Fa Zhou; Fei Yang; Qing-Xiang Guo; Song Xue

doi:10.1055/s-2007-984904

LETTER

DMAP-Catalyzed Benzannulation of Ethyl Propiolate with β-Dicarbonyl Moieties

Qing-Fa Zhou, Fei Yang, Qing-Xiang Guo, Song Xue*
Department of Chemistry, University of Science and Technology of China, Hefei 230026, P. R. of China
Fax: +86(551)3606689; e-Mail: xuesong@ustc.edu.cn;

Abstract

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Abstract

4-Dimethylaminopyridine (DMAP)-catalyzed benzannulation reaction of ethyl propiolate with β-dicarbonyl compounds at room temperature providing highly substituted benzenes is described.

Key words

ethyl propiolate - DMAP - benzannulation - β-dicarbonyl compounds

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References

References and Notes

<A NAME="RW09807ST-1A">1a</A> Modern Arene Chemistry Astruc D. Wiley-VCH; Weinheim / Germany: 2002.

<A NAME="RW09807ST-1B">1b</A> The Chemistry of Phenols Rappoport Z. Wiley-VCH; New York: 2003.

<A NAME="RW09807ST-2A">2a</A> Bunnet JF. Acc. Chem. Res. 1978, 11: 413

<A NAME="RW09807ST-2B">2b</A> Miyaura N. Suzuki A. Chem. Rev. 1995, 95: 2457

<A NAME="RW09807ST-2C">2c</A> Chauder B. Green L. Snieckus V. Pure Appl. Chem. 1999, 71: 1521

<A NAME="RW09807ST-3A">3a</A> Kotha T. Brahmachary E. Lahiri K. Eur. J. Org. Chem. 2005, 4741

<A NAME="RW09807ST-3B">3b</A> Saito S. Yamamoto Y. Chem. Rev. 2000, 100: 2901

<A NAME="RW09807ST-3C">3c</A> Vollhardt KPC. Angew. Chem., Int. Ed. Engl. 1984, 23: 539

<A NAME="RW09807ST-4A">4a</A> Oppolzer W. In Comprehensive Organic Synthesis Vol. 5: Trost BM. Fleming I. Pergamon; Oxford: 1991. p.315-399

<A NAME="RW09807ST-4B">4b</A> Xi Z. Sato K. Gao Y. Lu J. Takahashi T. J. Am. Chem. Soc. 2003, 125: 9568

<A NAME="RW09807ST-4C">4c</A> Takahashi T. Ishikawa M. Huo S. J. Am. Chem. Soc. 2002, 124: 388

<A NAME="RW09807ST-4D">4d</A> Langer P. Bose G. Angew. Chem. Int. Ed. 2003, 42: 4033

<A NAME="RW09807ST-4E">4e</A> Katritzky AR. Li J. Xie L. Tetrahedron 1999, 55: 8263

<A NAME="RW09807ST-5">5</A> Dotz KH. Tomuschat P. Chem. Soc. Rev. 1999, 28: 187

<A NAME="RW09807ST-6A">6a</A> Tius MA. Gomez-Galeno J. Tetrahedron Lett. 1986, 27: 2571

<A NAME="RW09807ST-6B">6b</A> Chan TH. Prasad CVC. J. Org. Chem. 1986, 51: 3012

<A NAME="RW09807ST-7A">7a</A> Serra S. Fuganti C. Moro A. J. Org. Chem. 2001, 66: 7883

<A NAME="RW09807ST-7B">7b</A> Turnbull P. Moore HW. J. Org. Chem. 1995, 60: 644

<A NAME="RW09807ST-8A">8a</A> Nefzi A. Ostresh JM. Houghten RA. Chem. Rev. 1997, 97: 449

<A NAME="RW09807ST-8B">8b</A> Simon C. Constantieux T. Rodriguez J. Eur. J. Org. Chem. 2004, 4957

<A NAME="RW09807ST-8C">8c</A> Li C. Chem. Rev. 2005, 105: 3095

<A NAME="RW09807ST-8D">8d</A> Xue S. Zhou Q.-F. Li L.-Z. Guo Q.-X. Synlett 2005, 2990

<A NAME="RW09807ST-9A">9a</A> Hanedanian M. Loreau O. Sawiki M. Taran F. Tetrahedron 2005, 61: 2287

<A NAME="RW09807ST-9B">9b</A> Xue S. Zhou Q.-F. Zheng X.-Q. Synth. Commun. 2005, 35: 3027

<A NAME="RW09807ST-9C">9c</A> Trost BM. Dake GR. J. Am. Chem. Soc. 1997, 119: 7595

<A NAME="RW09807ST-10">10</A> We recently reported cyclotrimerization of acetylenic ketones catalyzed by DMAP in the presence of 2,4-pentanedione: Zhou Q.-F. Yang F. Guo Q.-X. Xue S. Synlett 2007, 215

For selective recent phosphine- and amine-catalyzed heterocyclization, see:

<A NAME="RW09807ST-11A">11a</A> Xu Z. Lu X. Tetrahedron Lett. 1997, 38: 3461

<A NAME="RW09807ST-11B">11b</A> Xu Z. Lu X. J. Org. Chem. 1998, 63: 5031

<A NAME="RW09807ST-11C">11c</A> Lu X. Zhang C. Xu Z. Acc. Chem. Res. 2001, 34: 535 ; and references therein

<A NAME="RW09807ST-11D">11d</A> Du Y. Lu X. Yu Y. J. Org. Chem. 2002, 67: 8901

<A NAME="RW09807ST-11E">11e</A> Zhu X.-F. Lah J. Kwon O. J. Am. Chem. Soc. 2003, 125: 4716

<A NAME="RW09807ST-11F">11f</A> Zhu X.-F. Henry CE. Wang J. Dudding T. Kwon O. Org. Lett. 2005, 7: 1387

<A NAME="RW09807ST-11G">11g</A> Zhu X.-F. Henry CE. Wang J. Dudding T. Kwon O. Org. Lett. 2005, 7: 2977

<A NAME="RW09807ST-11H">11h</A> Shi Y.-L. Shi M. Org. Lett. 2005, 7: 3057

<A NAME="RW09807ST-11I">11i</A> Zhao GL. Shi M. J. Org. Chem. 2005, 70: 9975

<A NAME="RW09807ST-11J">11j</A> Bi X. Dong D. Liu Q. Pan W. Zhao L. Li B. J. Am. Chem. Soc. 2005, 127: 4578

<A NAME="RW09807ST-11K">11k</A> Cui S.-J. Lin X.-F. Wang Y.-G. Eur. J. Org. Chem. 2006, 5174

<A NAME="RW09807ST-11L">11l</A> Wang Y.-G. Cui S.-L. Lin X.-F. Org. Lett. 2006, 8: 1241

Typical Procedure: A round-bottomed flask, equipped with a stirring bar, was charged with β-dicarbonyl moieties (0.3 mmol) and DMAP (0.06 mmol) in CH₂Cl₂ (3 mL) followed by ethyl propiolate (0.66 mmol) via a syringe. After stirring for the specific time at r.t., the reaction was concentrated under reduced pressure on a rotary evaporator and purified by silica gel chromatography using PE-EtOAc (10:1-5:1) to afford the corresponding product. Compound 3a: ¹H NMR (300 MHz, CDCl₃): δ = 8.39 (d, J = 1.7 Hz, 1 H), 8.18 (d, J = 1.7 Hz, 1 H), 4.30-4.39 (m, 4 H), 2.57 (s, 3 H), 2.55 (s, 3 H), 1.37 (t, J = 7.8 Hz, 6 H). ¹³C NMR (75 Hz, CDCl₃): δ = 202.3, 167.2, 165.2, 142.1, 141.8, 133.7, 132.7, 130.9, 128.2, 61.71, 61.68, 30.7, 18.2, 14.4, 14.3. IR (neat): 1725, 1259 cm^-1. HRMS (ESI): m/z [M⁺] calcd for C₁₅H₁₈O₅: 278.1154; found: 278.1147.
Compound 7a: ¹H NMR (300 MHz, CDCl₃): d = 8.01 (d, J = 15.8 Hz, 1 H), 7.69 (s, 1 H), 7.55 (d, J = 7.9 Hz, 2 H), 7.34-7.43 (m, 4 H), 5.84 (dd, J = 3.2, 10.2 Hz, 1 H), 4.23-4.35 (m, 4 H), 4.15-4.19 (m, 2 H), 2.86 (dd, J = 10.2, 15.2 Hz, 1 H), 2.54 (dd, J = 3.2, 15.2 Hz, 1 H), 1.31-1.41 (m, 6 H), 1.24 (t, J = 7.2 Hz, 3 H). ¹³C NMR (75 MHz, CDCl₃): d = 169.6, 165.0, 164.3, 162.1, 140.0, 136.0, 132.6, 129.9, 129.0, 128.2, 120.0, 117.9, 105.6, 71.9, 60.96, 60.92, 60.88, 37.8, 14.53, 14.45, 14.39. HRMS (EI): m/z [M⁺] calcd for C₂₃H₂₆O₇: 414.1679; found: 414.1674.
Compound 10a: ¹H NMR (300 MHz, CDCl₃): δ = 9.20 (d, J = 1.8 Hz, 1 H), 8.55 (d, J = 1.8 Hz, 1 H), 7.30 (m, 1 H), 7.12-7.17 (m, 2 H), 6.97-7.06 (m, 4 H), 6.87 (d, J = 7.5 Hz, 2 H), 4.49 (q, J = 7.2 Hz, 2 H), 3.99 (q, J = 7.2 Hz, 2 H), 2.33 (s, 3 H), 1.48 (t, J = 7.2 Hz, 3 H), 0.87 (t, J = 7.2 Hz, 3 H). ¹³C NMR (75 Hz, CDCl₃): δ = 166.7, 164.4, 144.8, 143.9, 142.1, 137.3, 136.6, 134.6, 134.2, 131.8, 130.5, 130.1, 129.2, 128.2, 127.9, 127.1, 62.1, 61.7, 21.6, 14.4, 13.6. IR (neat): 1727, 1248 cm^-1. HRMS (EI): m/z [M⁺] calcd for C₂₅H₂₄O₆S: 452.1294; found: 452.1302.