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Synlett 2008(20): 3226-3230  
DOI: 10.1055/s-0028-1087369
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

On the Way to an Oxidative Hosomi-Sakurai Reaction

Cyrille Sabot, Bruno Commare, Marc-Alexandre Duceppe, Salima Nahi, Kimiaka C. Guérard, Sylvain Canesi*
Laboratoire de Méthodologie et Synthèse de Produits Naturels, Université du Québec à Montréal, C.P. 8888, Succ. Centre-Ville, Montréal, Québec H3C 3P8, Canada
Fax: +1(514)9874054; e-Mail: canesi.sylvain@uqam.ca;
Further Information

Publication History

Received 18 August 2008
Publication Date:
26 November 2008 (online)

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Abstract

An oxidative allylation process mediated by a hyper­valent iodine reagent has been performed on polysubstituted phenols. This reaction, occurring in useful to good yields, leads to a rapid access to dienones containing a quaternary carbon center.

Key words

hypervalent iodine - allyltrimethylsilane - substitued phenols - oxidative allylation

    References and Notes

  • 1 Hosomi A. Sakurai H. Tetrahedron Lett.  1976,  1295 
    CrossrefGoogle Scholar
  • 2a Tamura Y. Yakura T. Haruta J. Kita Y. J. Org. Chem.  1987,  52:  3927 
    Google Scholar
  • 2b Kita Y. Tohma H. Hatanaka K. Takada T. Fujita S. Mitoh S. Sakurai H. Oka S. J. Am. Chem. Soc.  1994,  116:  3684 
    Google Scholar
  • 2c Kita Y. Takada T. Gyoten M. Tohma H. Zenk MH. Eichhorn J. J. Org. Chem.  1996,  61:  5854 
    Google Scholar
  • 2d Kita Y. Gyoten M. Ohtsubo M. Tohma H. Takada T. Chem. Commun.  1996,  1481 
    Google Scholar
  • 2e Takada T. Arisawa M. Gyoten M. Hamada R. Tohma H. Kita Y. J. Org. Chem.  1998,  63:  7698 
    Google Scholar
  • 2f Arisawa M. Utsumi S. Nakajima M. Ramesh NG. Tohma H. Kita Y. Chem. Commun.  1999,  469 
    Google Scholar
  • 2g Akai S. Kawashita N. Morita N. Nakamura Y. Iio K. Kita Y. Heterocycles  2002,  58:  75 
    Google Scholar
  • 2h Dohi T. Maruyama A. Takenaga N. Senami K. Minamitsuji Y. Fujioka H. Caemmerer SB. Kita Y. Angew. Chem. Int. Ed.  2008,  47:  3787 
    Google Scholar
  • 3a Moreno I. Tellitu I. SanMartín R. Domínguez E. Synlett  2001,  1161 
    Google Scholar
  • 3b Tohma H. Iwata M. Maegawa T. Kita Y. Tetrahedron Lett.  2002,  43:  9241 
    Google Scholar
  • 3c Akai S. Kawashita N. Morita N. Nakamura Y. Iio K. Kita Y. Heterocycles  2002,  58:  75 
    Google Scholar
  • 3d Tohma H. Iwata M. Maegawa T. Kiyono Y. Maruyama A. Kita Y. Org. Biomol. Chem.  2003,  1:  1647 
    Google Scholar
  • 3e Dohi T. Morimoto K. Kiyono Y. Maruyama A. Tohma H. Kita Y. Chem. Commun.  2005,  2930 
    Google Scholar
  • 3f Dohi T. Morimoto K. Maruyama A. Kita Y. Org. Lett.  2006,  8:  2007 
    Google Scholar
  • 4a Pelter A. Drake RA. Tetrahedron Lett.  1988,  29:  4181 
    Google Scholar
  • 4b Gates BD. Dalidowicz P. Tebben A. Wang S. Swenton JS. J. Org. Chem.  1992,  57:  2135 
    Google Scholar
  • 4c Quideau S. Pouységu L. Looney MA. J. Org. Chem.  1998,  63:  9597 
    Google Scholar
  • 4d Quideau S. Looney MA. Pouységu L. Org. Lett.  1999,  1:  1651 
    Google Scholar
  • 4e Quideau S. In Modern Arene Chemistry   Astruc D. Wiley-VCH; Weinheim: 2002.  p.539 
    Google Scholar
  • 4f Quideau S. Pouységu L. Deffieux D. Curr. Org. Chem.  2004,  8:  113 
    Google Scholar
  • 4g Ciufolini MA. Canesi S. Ousmer M. Braun NA. Tetrahedron  2006,  62:  5318 
    Google Scholar
  • 4h Nicolaou KC. Edmonds DJ. Li A. Tria GS. Angew. Chem.  2007,  119:  4016 
    Google Scholar
  • 4i Ciufolini MA. Braun NA. Canesi S. Ousmer M. Chang J. Chai D. Synthesis  2007,  3759 
    Google Scholar
  • 4j Bérard D. Jean A. Canesi S. Tetrahedron Lett.  2007,  48:  8238 
    Google Scholar
  • 4k Bérard D. Giroux MA. Racicot L. Sabot C. Canesi S. Tetrahedron  2008,  7537 
    Google Scholar
  • 4l Quideau S. Pouységu L. Deffieux D. Synlett  2008,  467 
    Google Scholar
  • 4m Pouységu L. Chassaing S. Dejugnac D. Lamidey AM. Miqueu K. Sotiropoulos JM. Quideau S. Angew. Chem. Int. Ed.  2008,  47:  3552 
    Google Scholar
  • 4n Liang H. Ciufolini MA. J. Org. Chem.  2008,  4299 
    Google Scholar
  • 5 Jean A. Cantat J. Bérard D. Bouchu D. Canesi S. Org. Lett.  2007,  9:  2553 
    CrossrefGoogle Scholar
  • 6a Kita Y. Tohma H. Kikuchi K. Inagaki M. Yakura T. J. Org. Chem.  1991,  56:  435 
    Google Scholar
  • 6b Hamamoto H. Anilkumar G. Tohma H. Kita Y. Chem. Eur. J.  2002,  8:  5377 
    Google Scholar
  • 7 Nicolaou KC. Edmonds DJ. Li A. Tria GS. Angew. Chem.  2007,  119:  4016 
    CrossrefGoogle Scholar
  • 8a Quideau S. Looney MA. Pouységu L. Org. Lett.  1999,  1:  1651 
    Google Scholar
  • 8b Quideau S. Pouységu L. Oxoby M. Looney MA. Tetrahedron  2001,  57:  319 
    Google Scholar
  • 9a Canesi S. Bouchu D. Ciufolini MA. Angew. Chem. Int. Ed.  2004,  43:  4336 
    Google Scholar
  • 9b Imbos R. Minnaard AJ. Feringa BL. J. Am. Chem. Soc.  2002,  124:  184 
    Google Scholar
  • 9c Hayashi Y. Gotoh H. Tamura T. Yamaguchi H. Masui R. Shoji M. J. Am. Chem. Soc.  2005,  127:  16028 
    Google Scholar
  • 9d Liu Q. Rovis T. J. Am. Chem. Soc.  2006,  128:  2552 
    Google Scholar
  • 9e Vo NT. Pace RDM. O’Hara F. Gaunt MJ. J. Am. Chem. Soc.  2008,  130:  404 
    Google Scholar
  • 10a Kobayashi S. Shingu T. Uyeo S. Chem. Ind.  1956,  177 
    Google Scholar
  • 10b Fan C. Tu Y. Song ZL. Zhang E. Shi L. Wang M. Wang B. Zhang SY. Org. Lett.  2004,  6:  4691 
    Google Scholar
  • 11 Nicolaou KC. Scott Tria G. Edmonds DJ. Angew. Chem. Int. Ed.  2008,  47:  1780 
    CrossrefGoogle Scholar
  • 12 Bérard D. Racicot L. Sabot C. Canesi S. Synlett  2008,  1076 
    Article in Thieme ConnectGoogle Scholar
  • 13 Ozanne-Beaudenon A. Quideau S. Angew. Chem. Int. Ed.  2005,  44:  7065 
    CrossrefGoogle Scholar
  • 15 Clemo GR. Haworth RD. Walton E. J. Chem. Soc.  1930,  1110 
    Google Scholar
  • 16 Thadani AN. Huang Y. Rawal VH. Org. Lett.  2007,  9:  3873 
    CrossrefGoogle Scholar
  • 19 Fleming I. Roessler F. J. Chem. Soc., Chem. Commun.  1980,  276 
    CrossrefGoogle Scholar
14

Analytical Data
IR: ca. 1645 (CO) cm-¹.
Compound 13b: ¹H NMR (300 MHz, CDCl3): δ = 6.33 (s,
2 H), 5.43 (m, 1 H), 4.92 (m, 2 H), 2.23 (d, 2 H, J = 7.8 Hz), 1.53 (m, 2 H), 1.19 (m, 22 H), 0.99 (m, 2 H), 0.80 (t, 3 H,
J = 6.6 Hz). ¹³C NMR (150 MHz, CDCl3): δ = 187.3, 148.2, 145.7, 133.5, 118.1, 45.3, 44.1, 40.1, 35.1, 32.4, 29.9, 24.3, 22.7, 14.2. ESI-HRMS: m/z calcd for C22H36ONa [M + Na]+: 339.2658; found: 339.2662.
Compound 13c: ¹H NMR (300 MHz, CDCl3): δ = 6.39 (s,
2 H), 5.43 (m, 1 H), 4.93 (m, 2 H), 2.32 (d, 2 H, J = 7.5 Hz), 1.83 (h, 1 H, J = 6.6 Hz), 1.21 (s, 18 H), 0.84 (d, 6 H, J = 6.6 Hz). ¹³C NMR (150 MHz, CDCl3): δ = 187.4, 148.8, 144.3, 133.8, 117.8, 46.4, 42.4, 36.3, 35.3, 29.9, 18.2. ESI-HRMS: m/z calcd for C20H33O [M + H]+: 289.2525; found: 289.2529.
Compound 13d: ¹H NMR (300 MHz, CDCl3): δ = 6.44 (s, 2 H), 5.48 (m, 1 H), 4.97 (m, 2 H), 3.42 (t, 2 H, J = 7.2 Hz), 2.30 (d, 2 H, J = 7.8 Hz), 1.92 (t, 2 H, J = 7.2 Hz), 1.27 (s, 18 H). ¹³C NMR (150 MHz, CDCl3): δ = 186.9, 148.4, 145.0, 132.7, 118.8, 60.0, 45.4, 42.9, 42.8, 35.2, 29.8 ESI-HRMS: m/z calcd for C19H30O2Na [M + Na]+: 313.2138; found: 313.2138.
Compound 13e: ¹H NMR (300 MHz, CDCl3): δ = 6.50 (s,
2 H), 5.49 (m, 1 H), 4.97 (m, 2 H), 3.48 (s, 2 H), 2.35 (d,
2 H, J = 7.2 Hz), 1.22 (s, 18 H), 0.88 (s, 9 H), 0.03 (s, 6 H). ¹³C NMR (150 MHz, CDCl3): δ = 187.2, 148.8, 143.0, 133.4, 118.3, 69.1, 45.7, 40.5, 35.2, 29.9, 26.1, 18.5, -5,1. ESI-HRMS: m/z calcd for C24H43O2Si [M + H]+: 391.3026; found: 391.3008.
Compound 13f: ¹H NMR (300 MHz, CDCl3): δ = 7.56 (d,
2 H, J = 7.5 Hz), 7.20 (d, 2 H, J = 7.5 Hz), 6.25 (s, 2 H), 5.35 (m, 1 H), 4.87 (m, 2 H), 4.29 (m, 1 H), 2.55 (q, 2 H, J = 6.6 Hz), 2.32 (s, 3 H), 2.17 (d, 2 H, J = 7.5 Hz), 1.79 (t, 2 H, J = 6.6 Hz), 1.10 (s, 18 H). ¹³C NMR (150 MHz, CDCl3): δ = 186.5, 149.1, 144.2, 144.0, 136.6, 132.3, 130.1, 127.3, 119.0, 45.3, 43.1, 40.1, 39.7, 35.2, 29.8, 21.8. ESI-HRMS: m/z calcd for C26H37NO3SNa [M + Na]+: 466.2386; found: 466.2378.
Compound 13g: ¹H NMR (300 MHz, CDCl3): δ = 6.49 (s,
2 H), 5.50 (m, 1 H), 4.01 (m, 2 H), 3.54 (s, 3 H), 2.54 (s, 2 H), 2.35 (d, 2 H, J = 7.2 Hz), 1.21 (s, 18 H). ¹³C NMR (150 MHz, CDCl3): δ = 186.7, 170.7, 148.1, 143.4, 132.5, 119.3, 51.7, 44.6, 44.3, 42.0, 35.2, 29.8. ESI-HRMS: m/z calcd for C20H31O3 [M + H]+: 319.2267; found: 319.2267.

17

Analytical Data Compound 17a: ¹H NMR (300 MHz, CDCl3): δ = 6.86 (s,
2 H), 5.52 (m, 1 H), 4.99 (m, 2 H), 2.26 (d, 2 H, J = 7.2 Hz), 1.20 (s, 3 H), 0.16 (s, 18 H). ¹³C NMR (150 MHz, CDCl3):
δ = 192.0, 162.4, 140.7, 133.3, 118.6, 45.2, 41.4, 25.5, -0.9. ESI-HRMS: m/z calcd for C16H29OSi2 [M + H]+: 293.1751; found: 293.1753.
Compound 17b: ¹H NMR (300 MHz, CDCl3): δ = 6.77 (s,
2 H), 5.51 (m, 1 H), 4.99 (dd, 1 H, J = 8.7, 1.2 Hz), 4.96 (dd, 1 H, J = 18.0, 1.2 Hz), 2.29 (d, 2 H, J = 7.2 Hz), 1.63 (q,
2 H, J = 7.8 Hz), 0.68 (t, 3 H, J = 7.8 Hz), 0.16 (s, 18 H). ¹³C NMR (150 MHz, CDCl3): δ = 192.4, 161.3, 143.0, 133.3, 118.3, 46.1, 44.3, 32.1, 9.3, -0.8. ESI-HRMS: m/z calcd for C17H31OSi2 [M + H]+: 307.1908; found: 307.1909.
Compound 17c: ¹H NMR (300 MHz, CDCl3): δ = 7.30 (m,
5 H), 7.00 (s, 2 H), 5.56 (m, 1 H), 5.05 (m, 2 H), 2.80 (d,
2 H, J = 7.2 Hz), 0.18 (18 H). ¹³C NMR (150 MHz, CDCl3): δ = 192.1, 160.7, 141.1, 140.8, 132.9, 129.3, 127.6, 127.0, 119.0, 48.6, 42.3, -0.9. ESI-HRMS: m/z calcd for C21H31OSi2 [M + H]+: 355.1908; found: 355.1914.
Compound 17d: ¹H NMR (300 MHz, CDCl3): δ = 6.86 (s,
2 H), 5.47 (m, 1 H), 4.98 (m, 2 H), 3.42 (t, 2 H, J = 6.9 Hz), 2.29 (d, 2 H, J = 7.2 Hz), 1.92 (t, 2 H, J = 6.9 Hz), 0.14 (s, 18 H). ¹³C NMR (150 MHz, CDCl3): δ = 192.1, 160.9, 142.7, 132.5, 119.1, 60.0, 44.7, 44.4, 42.0, -0.9. ESI-HRMS: m/z calcd for C17H31O2Si2 [M + H]+: 323.1857; found: 323.1853.

18

Analytical Data
Compound 21a: ¹H NMR (300 MHz, CDCl3): δ = 6.91 (d,
1 H, J = 2.7 Hz), 6.55 (1 H, d, J = 2.7 Hz), 5.55 (m, 1 H), 5.04 (m, 2 H), 2.34 (d, 2 H, J = 8.1 Hz), 1.27 (s, 3 H), 1.23 (s,
9 H). ¹³C NMR (150 MHz, CDCl3): δ = 179.1, 149.1, 149.0, 145.4, 133.8, 132.5, 119.5, 45.3, 42.9, 35.3, 29.5, 25.6. ESI-HRMS: m/z calcd for C14H20ClO [M + H]+: 239.1197; found: 239.1185.
Compound 21b: ¹H NMR (300 MHz, CDCl3): δ = 7.18 (d,
1 H, J = 3.0 Hz), 6.56 (d, 1 H, J = 3.0 Hz), 5.53 (m, 1 H), 5.04 (m, 2 H), 2.33 (d, 2 H, J = 6.9 Hz), 1.27 (s, 3 H), 1.22 (s,
9 H). ¹³C NMR (150 MHz, CDCl3): δ = 178.9, 153.6, 149.0, 145.1, 132.5, 126.4, 119.5, 45.1, 44.4, 35.4, 29.5, 25.5. ESI-HRMS: m/z calcd for C14H20BrO [M + H]+: 283.0692; found: 283.0688.
Compound 21c: ¹H NMR (300 MHz, CDCl3): δ = 7.50 (d,
1 H, J = 2.7 Hz), 6.57 (d, 1 H, J = 2.7 Hz), 5.54 (m, 1 H), 5.04 (m, 2 H), 2.32 (d, 1 H, J = 6.9 Hz), 2.29 (d, 1 H, J = 7.8 Hz), 1.27 (s, 3 H), 1.21 (s, 9 H). ¹³C NMR (150 MHz, CDCl3):
δ = 179.6, 161.9, 149.3, 143.8, 132.5, 119.5, 107.6, 46.1, 45.0, 35.5, 29.5, 25.3. ESI-HRMS: m/z calcd for C14H20IO [M + H]+: 331.0553; found: 331.0549.
Compound 21d: ¹H NMR (300 MHz, CDCl3): δ = 7.16 (d,
1 H, J = 2.7 Hz), 6.55 (1 H, d, J = 2.7 Hz), 5.47 (m, 1 H), 5.01 (m, 2 H), 2.40 (m, 2 H), 1.93 (hept, 1 H, J = 6.6 Hz), 0.93 (d, 3 H, J = 6.6 Hz), 0.89 (d, 3 H, J = 6.6 Hz). ¹³C NMR (150 MHz, CDCl3): δ = 179.3, 151.8, 147.4, 147.1, 132.6, 127.6, 119.1, 51.4, 41.8; 36.2, 35.7, 29.6, 18.4, 18.2. ESI-HRMS: m/z calcd for C16H23BrO2Na [M + Na]+: 333.0824; found: 333.0822.
Compound 21e: ¹H NMR (300 MHz, CDCl3): δ = 7.21 (d,
1 H, J = 3.0 Hz), 6.89 (d, 1 H, J = 3.0 Hz), 5.55 (m, 1 H), 5.05 (m, 2 H), 2.33 (d, 2 H, J = 7.2 Hz), 1.27 (s, 3 H), 0.18 (s,
9 H). ¹³C NMR (150 MHz, CDCl3): δ = 181.7, 162.9, 154.9, 139.6, 132.3, 125.4, 119.6, 46.0, 44.7, 25.0, -1.1. ESI-HRMS: m/z calcd for C13H19BrOSiNa [M + Na]+: 321.0280; found: 321.0278.
Compound 21f: ¹H NMR (300 MHz, CDCl3): δ = 7.16 (d,
1 H, J = 2.7 Hz), 6.84 (d, 1 H, J = 2.7 Hz), 5.53 (m, 1 H), 5.03 (m, 2 H), 2.35 (d, 2 H, J = 7.2 Hz), 1.65 (t, 2 H, J = 9.0 Hz), 1.25 (m, 2 H), 1.10 (m, 2 H), 0.85 (t, 3 H, J = 7.2 Hz), 0.19 (s, 9 H). ¹³C NMR (150 MHz, CDCl3): δ = 182.1, 162.4, 154.3, 141.3, 132.2, 126.1, 119.4, 50.4, 44.1, 38.9, 27.2, 23.3, 14.1, -1.1. ESI-HRMS: m/z calcd for C16H25BrOSiNa [M + Na]+: 363.0750; found: 363.0752.

20

Analytical Data
Compound 29a: ¹H NMR (300 MHz, CDCl3): δ = 6.52 (s,
2 H), 2.33 (d, 2 H, J = 2.3 Hz), 2.03 (t, 1 H, J = 2.3 Hz), 1.28 (s, 3 H), 1.23 (s, 9 H). ¹³C NMR (150 MHz, CDCl3): δ = 186.1, 146.6, 144.7, 79.8, 71.2, 38.5, 34.6, 30.9, 29.4, 25.3. ESI-HRMS: m/z calcd for C18H27O [M + H]+: 259.2056; found: 259.2042.
Compound 29h: ¹H NMR (300 MHz, CDCl3): δ = 6.44 (s,
2 H), 2.34 (d, 2 H, J = 2.3 Hz), 2.00 (t, 1 H, J = 2.3 Hz), 1,68 (t, 2 H, J = 8.2 Hz), 1.23 (s + q, 20 H, J = 8.2 Hz), 1.00 (sext, 2 H, J = 8.2 Hz), 0.84 (t, 3 H, J = 8.2 Hz). ¹³C NMR (150 MHz, CDCl3): δ = 186.5, 148.1, 143.8, 79.7, 71.1, 42.3, 38.3, 34.8, 30.2, 29.4, 26.5, 22.9, 13.8. ESI-HRMS: m/z calcd for C21H33O [M + H]+: 301.2526; found: 301.2533.
Compound 29i: ¹H NMR (300 MHz, CDCl3): δ = 6.44 (s,
2 H), 5,73 (m, 1 H), 4.96 (d, 1 H, J = 18.7 Hz), 4,93 (d, 1 H, J = 10.5 Hz), 2.37 (d, 2 H, J =2.3 Hz), 2.03 (t, 1 H, J = 2.3 Hz), 1.81 (t, 2 H, J = 8.2 Hz), 1.43 (t, 2 H, J = 8.2 Hz), 1.24 (s, 18 H). ¹³C NMR (150 MHz, CDCl3): δ = 186.4, 148.5, 143.3, 127.6, 114.8, 79.5, 71.4, 42.2, 37.7, 34.9, 30.4, 29.4, 28.8. ESI-HRMS: m/z calcd for C21H31O [M + H]+: 299.2369; found: 299.2376.