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Synlett 2011(3): 415-419  
DOI: 10.1055/s-0030-1259313
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Fe(OTf)3-Catalyzed Reaction of Benzylic Acetates with Organosilicon Compounds

Li Yan Chan, Sundae Kim, Wan Ting Chung, Chong Long, Sunggak Kim*
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore
Fax: +6567911961; e-Mail: sgkim@ntu.edu.sg;
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Publikationsverlauf

Received 20 October 2010
Publikationsdatum:
13. Januar 2011 (online)

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Abstract

Fe(OTf)3-catalyzed reaction of benzylic acetates with allyltrimethylsilane, azidotrimethylsilane, and cyanotrimethylsilane afforded the corresponding allylated, azido, and cyano products in high yields. 2-Trimethylsilyl-substituted benzofuran and indole worked well to furnish the benzyl-substituted benzofuran and indoles.

Key words

iron-catalyzed reaction - allylation - azidation - cyanation - benzylic acetates - organosilanes

    References and Notes

  • 1 Acid Catalysis in Modern Organic Synthesis   Vol. 1 and 2:  Yamamoto H. Ishihara K. Wiley-VCH; Weinheim: 2008. ; and references cited therein
  • 2a Cella JA. J. Org. Chem.  1982,  47:  2125 
    Suche in Google Scholar
  • 2b Park DH. Kim SH. Kim SM. Kim JD. Kim YH. Chem. Commun.  1999,  963 
  • 2c Capaccio CAI. Varela O. Tetrahedron Lett.  2003,  44:  4023 
    Suche in Google Scholar
  • 2d Rajamaki S. Kilburn JD. Chem. Commun.  2005,  1637 
  • 2e Kimta Y. Matsuda S. Ganesh JK. Fujioka H. J. Org. Chem.  2006,  71:  5191 
    Suche in Google Scholar
  • 3a Kaur G. Kausik M. Trehan S. Tetrahedron Lett.  1997,  38:  2521 
    Suche in Google Scholar
  • 3b Wabnitz TC. Spencer JB. Org. Lett.  2003,  5:  2141 
    Suche in Google Scholar
  • 3c Wabnitz TC. Yu J.-Q. Spencer JB. Chem. Eur. J.  2004,  10:  484 
    Suche in Google Scholar
  • 3d Pihko PM. Angew. Chem. Int. Ed.  2004,  43:  2062 
    Suche in Google Scholar
  • 3e Sun J. Kozmin SA. J. Am. Chem. Soc.  2005,  127:  13512 
    Suche in Google Scholar
  • For reviews, see:
  • 4a Nair V. Mathew J. Prabhakara J. Chem. Soc. Rev.  1997,  127 
  • 4b Ranu BC. Eur. J. Org. Chem.  2000,  2347 
  • 4c Nair V. Ros S. Jayan CN. Pillai BS. Tetrahedron  2004,  60:  1959 
    Suche in Google Scholar
  • 4d Lee PH. Bull. Korean Chem. Soc.  2007,  28:  17 
    Suche in Google Scholar
  • For additional selected reports, see:
  • 4e Loh T.-P. Wei L.-L. Tetrahedron  1998,  54:  7615 
    Suche in Google Scholar
  • 4f Loh T.-P. Hu Q.-Y. Ma L.-T. J. Am. Chem. Soc.  2001,  123:  2450 
    Suche in Google Scholar
  • 4g Yasuda M. Saito T. Ueba M. Baba A. Angew. Chem. Int. Ed.  2004,  43:  1414 
    Suche in Google Scholar
  • 4h Saito T. Nishimoto Y. Yasuda M. Baba A. J. Org. Chem.  2006,  71:  8516 
    Suche in Google Scholar
  • 4i Yasuda M. Somyo T. Baba A. Angew. Chem. Int. Ed.  2006,  45:  793 
    Suche in Google Scholar
  • 4j Nishimoto Y. Yasuda M. Baba A. Org. Lett.  2007,  9:  4931 
    Suche in Google Scholar
  • 4k Yadav JS. Reddy BVS. Aravind S. Kumar GKSN. Reddy AS. Tetrahedron Lett.  2007,  48:  6117 
    Suche in Google Scholar
  • 4l Nishimoto Y. Moritoh R. Yasuda M. Baba A. Angew. Chem. Int. Ed.  2009,  48:  577 
    Suche in Google Scholar
  • For reviews, see:
  • 5a Leonard NM. Wieland LC. Mohan RS. Tetrahedron  2002,  58:  8373 
    Suche in Google Scholar
  • 5b Gaspard-Iloughmane H. Le Roux C. Eur. J. Org. Chem.  2004,  12:  2517 
    Suche in Google Scholar
  • For further selected reports, see:
  • 5c Matsuhita Y.-I. Sugamoto K. Matsui T. Tetrahedron Lett.  2004,  45:  4723 
    Suche in Google Scholar
  • 5d De S K. Gibbs RA. Tetrahedron Lett.  2005,  46:  8345 
    Suche in Google Scholar
  • 5e Evans PA. Andrews WJ. Tetrahedron Lett.  2005,  46:  5625 
    Suche in Google Scholar
  • 5f Garrigues B. Gonzaga F. Robert H. Dubac J. J. Org. Chem.  1997,  62:  4880 
    Suche in Google Scholar
  • 5g Ollevier T. Nadeau E. Eguillon JC. Adv. Synth. Catal.  2006,  348:  2080 
    Suche in Google Scholar
  • 5h Qin H. Yamagiwa N. Matsunaga S. Shibasaki M. J. Am. Chem. Soc.  2006,  128:  1611 
    Suche in Google Scholar
  • 6a Tsuchimoto T. Maeda T. Shirakawa E. Kawakami Y. Chem. Commun.  2000,  1573 
  • 6b Hanawa H. Kii S. Asao N. Maruoka K. Tetrahedron Lett.  2000,  41:  5543 
    Suche in Google Scholar
  • 6c Yamasaki S. Kanai M. Shibasaki M. Chem. Eur. J.  2001,  7:  4066 
    Suche in Google Scholar
  • 6d Sharma GVM. Reddy KL. Lakshmi PS. Ravi R. Kunwar AC. J. Org. Chem.  2006,  71:  3967 
    Suche in Google Scholar
  • 6e Isoda T. Akiyama R. Oyamada H. Kobayashi S. Adv. Synth. Catal.  2006,  348:  1813 
    Suche in Google Scholar
  • 7a Jung ME. Maderna A. J. Org. Chem.  2004,  69:  7755 
    Suche in Google Scholar
  • 7b Shushizadeh MR. Kiany M. Chin. Chem. Lett.  2009,  20:  1068 
    Suche in Google Scholar
  • For reviews, see:
  • 8a Bolm C. Legros J. Paih JL. Zani L. Chem. Rev.  2004,  104:  6217 
    Suche in Google Scholar
  • 8b Iron Catalysis in Organic Chemistry: Reactions and Applications   Plietker B. Wiley-VCH; Weinheim: 2008. 
  • 8c Han J. Cui Z. Wang J. Liu Z. Synth. Commun.  2010,  40:  2042 
    Suche in Google Scholar
  • 9a Iovel I. Mertins K. Krischel J. Zapf A. Beller M. Angew. Chem. Int. Ed.  2005,  44:  3913 
    Suche in Google Scholar
  • 9b Li R. Wang SR. Lu W. Org. Lett.  2007,  9:  2219 
    Suche in Google Scholar
  • 9c Bandini M. Tragni M. Umani-Ronchi A. Adv. Synth. Catal.  2009,  351:  2521 
    Suche in Google Scholar
  • 9d Xu X. Xu X. Li H. Xie X. Li Y. Org. Lett.  2010,  12:  100 
    Suche in Google Scholar
  • 9e Wang B. Wang S. Li P. Wang L. Chem. Commun.  2010,  5891 
  • For reviews, see:
  • 10a Sherry BD. Fürstner A. Acc. Chem. Res.  2008,  41:  1500 
    Suche in Google Scholar
  • 10b Czaplik WM. Mayer M. Cvengros J. Wangelin AJV. ChemSusChem  2009,  2:  396 
    Suche in Google Scholar
  • For recent reports, see:
  • 10c Guerinot A. Reymond S. Cossy J. Angew. Chem. Int. Ed.  2007,  46:  6521 
    Suche in Google Scholar
  • 10d Kofink CC. Blank B. Pagano S. Gotz N. Knochel P. Chem. Commun.  2007,  1954 
  • 10e Cahiez G. Foulgoc L. Moyeux A. Angew. Chem. Int. Ed.  2009,  48:  2969 
    Suche in Google Scholar
  • 10f Bezier D. Darcel C. Adv. Synth. Catal.  2009,  351:  1732 
    Suche in Google Scholar
  • 10g Vallee F. Mousseau JJ. Charette AB. J. Am. Chem. Soc.  2010,  132:  1514 
    Suche in Google Scholar
  • 11a Watahiki T. Oriyama T. Tetrahedron Lett.  2002,  43:  8959 
    Suche in Google Scholar
  • 11b Watahiki T. Akabane Y. Mori S. Oriyama T. Org. Lett.  2003,  5:  3045 
    Suche in Google Scholar
  • 11c Durandetti M. Perichon J. Tetrahedron Lett.  2006,  47:  6255 
    Suche in Google Scholar
  • For selected reports, see:
  • 12a Michaux J. Terrasson V. Marque S. Wehbe J. Prim D. Campagne J.-M. Eur.
    J. Org. Chem.  2007,  2601 
  • 12b Jana U. Maiti S. Biswas S. Tetrahedron Lett.  2008,  49:  858 
    Suche in Google Scholar
  • 12c Mancheno OC. Dallimore J. Plant A. Bolm C. Org. Lett.  2009,  11:  2429 
    Suche in Google Scholar
  • 12d Li P. Zhang Y. Wang L. Chem. Eur. J.  2009,  15:  2045 
    Suche in Google Scholar
  • 12e Wu X.-F. Darcel C. Eur. J. Org. Chem.  2009,  4753 
  • 12f Yoshikai N. Matsumoto A. Norinder J. Nakamura E. Angew. Chem. Int. Ed.  2009,  48:  2925 
    Suche in Google Scholar
  • 12g Driller KM. Klein H. Jackstell R. Beller M. Angew. Chem. Int. Ed.  2009,  48:  6041 
    Suche in Google Scholar
  • 12h Thirupathi P. Kim SS. Tetrahedron  2010,  66:  2995 
    Suche in Google Scholar
  • 13a Kim S. Chung KN. Yang S. J. Org. Chem.  1987,  52:  3917 
    Suche in Google Scholar
  • 13b Sharma GVM. Kumar KR. Sreenivas P. Krishna PR. Chorghade MS. Tetrahedron: Asymmetry  2002,  13:  687 
    Suche in Google Scholar
  • 13c Kim SH. Shin C. Pai AN. Koh HK. Chang MH. Chung BY. Cho YS. Synthesis  2004,  1581 
  • 13d Terrassson V. Marque S. Georgy M. Campagne J.-M. Prim D. Adv. Synth. Catal.  2006,  348:  2063 
    Suche in Google Scholar
  • 16 Nishimoto Y. Kajioka M. Saito T. Yasuda M. Baba A. Chem. Commun.  2008,  6396 
14

Reaction of(methoxymethylene)dibenzene (Ph2CHOMe) with allyltrimethylsilane in the presence of 5 mol% Fe(OTf)3 in DCE at r.t. for 5 h afforded 4a (73%) but the allylation of 3 did not occur, even under prolonged heating at 80 ˚C.

15

Fe(OTf)3 was prepared from 5 mol% FeCl3 and 15 mol% AgOTf in DCE. Filtration was done to remove the AgCl precipitate, and the catalyst was used to repeat the allylation. The reaction time and yield observed were comparable to the Fe(OTf)3 generated in situ without filtration. For instance, the allylation of 4 under the similar conditions afforded 4a in 89% yield.

17

General Procedure for the Reaction of Benzylic Acetates with Organosilanes: But-3-ene-1,1-diyldibenzene (4a)
Anhydrous FeCl3 (2.4 mg, 0.015 mmol) and AgOTf (11.5 mg, 0.045 mmol) was carefully weighed inside a glove box and stirred in DCE (2 mL) for 5 min. Allyl trimethylsilane (41.1 mg, 0.36 mmol) and benzhydryl acetate 4 (67.9 mg, 0.3 mmol) were then added to the prepared catalyst solution and stirred for 0.5 h at r.t. The residual crude product was concentrated in vacuo and purified by silica gel column chromatography using n-hexane as eluent to afford the desired product 4a (60.0 mg, 96% yield). ¹H NMR (400 MHz, CDCl3): δ = 7.29-7.23 (m, 8 H), 7.19-7.15 (m, 2 H), 5.75-5.68 (m, 1 H), 5.05-4.93 (m, 2 H), 4.01 (t, J = 7.8 Hz, 1 H), 2.84-2.80 (m, 2 H). ¹³C NMR (100 MHz, CDCl3): δ = 144.5, 136.8, 128.4, 127.9, 126.2, 116.3, 51.2, 39.9.

18

¹ H NMR and ¹³ C NMR Data of Previously Unknown Compounds
2-Benzhydryl-1-methyl-1 H -indole (4g)
¹H NMR (400 MHz, CDCl3): δ = 7.29-7.17 (m, 13 H), 6.97 (t, J = 7.6 Hz, 1 H), 6.40 (s, 1 H), 5.66 (s, 1 H), 3.68 (s, 1 H). ¹³C NMR (100 MHz, CDCl3): δ = 144.1, 137.4, 129.0, 128.7, 128.2, 127.3, 126.1, 121.6, 120.0, 118.8, 118.2, 109.1, 48.8, 32.6. HRMS (EI+): m/z calcd for C22H20N [M + 1]: 298.1596; found: 298.1603.
2-(4-Methoxybenzyl)-1-methyl-1 H -indole (6d)
¹H NMR (400 MHz, CDCl3): δ = 7.51 (d, J = 7.6 Hz, 1 H), 7.29-7.18 (m, 4 H), 7.06 (t, J = 7.4 Hz, 1 H), 6.82 (d, J = 8.4 Hz, 2 H), 6.72 (s, 1 H), 4.04 (s, 2 H), 3.77 (s, 3 H), 3.71 (s, 3 H). ¹³C NMR (100 MHz, CDCl3): δ = 157.7, 137.1, 133.5, 129.5, 127.8, 127.0, 121.5, 119.2, 118.7, 114.7, 113.7, 109.1, 55.2, 32.6, 30.6, 29.2. HRMS (EI+): m/z calcd for C22H20N [M + 1]: 252.1388; found: 252.1393.
( E )-2-(1,3-Diphenylallyl)-1-methyl-1 H -indole (9d)
¹H NMR (400 MHz, CDCl3): δ = 7.42 (d, J = 8.0 Hz, 1 H), 7.37-7.18 (m, 13 H), 7.01 (t, J = 7.4 Hz, 1 H), 6.74-6.69 (m, 2 H), 6.43 (d, J = 16.0 Hz, 1 H), 5.11 (d, J = 7.6 Hz, 1 H), 3.72 (s, 3 H). ¹³C NMR (100 MHz, CDCl3): δ = 143.5, 137.5, 137.4, 132.7, 130.4, 128.4, 127.3, 127.2, 127.1, 126.3, 121.6, 120.0, 118.8, 117.0, 109.2, 46.1, 32.7. HRMS (EI+): m/z calcd for C24H22N [M + 1]: 324.1752; found: 324.1746.