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Synlett 2003(14): 2155-2158  
DOI: 10.1055/s-2003-42092
LETTER
© Georg Thieme Verlag Stuttgart · New York

Catalytic Hydrophosphination of Alkenylalkyl Ethers

Marina A. Kazankova, Mstislav O. Shulyupin, Irina P. Beletskaya*
Department of Chemistry, Moscow State University (MSU), Leninskie Gory 1, building 3, 119992 Moscow, Russia
Fax: +7(95)9393618; e-Mail: beletska@org.chem.msu.ru;
Further Information

Publication History

Received 4 August 2003
Publication Date:
15 October 2003 (online)

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Abstract

Hydrophosphination of alkenylalkyl ethers catalyzed by Pd- and Ni-complexes is described. The reaction is regioselective giving only Markovnikov product isolated as α-alkoxyalkyldiphenyl oxide after oxidation by H2O2.

Key words

nickel - palladium - alkenes - hydrophosphination - al­kenylalkyl ethers

    References

  • 1a The Chemistry of Organophosphorus Compounds   Hartley FR. Wiley; Chichester UK.: Vol. 1-4:  p.1990-1996  
    CrossrefGoogle Scholar
  • 1b Quin LD. A Guide to Organophosphorus Chemistry   Wiley; New York: 2000. 
    CrossrefGoogle Scholar
  • 1c Wicht DK. Glueck DS. In Catalytic Heterofunctionalization   Togni A. Grutzmacher H. Wiley-VCH; Weinheim: 2001.  Chap. 5. ; and references therein
    CrossrefGoogle Scholar
  • 1d Beletskaya IP. Kazankova MA. Russ. J. Org. Chem.  2002,  38:  1391 
    CrossrefGoogle Scholar
  • 2a Therrien B. Koning A. Warol TR. Organomatallics  1999,  18:  1565 
    Google Scholar
  • 2b Mitchell TN. Heesche KJ. J. Organomet. Chem.  1991,  409:  163 
    Google Scholar
  • 2c Therrien B. Ward TR. Angew. Chem. Int. Ed.  1999,  38:  405 
    Google Scholar
  • 2d Malisheva SF. Gusarova NK. Belogorodova NA. Nikitin MV. Gendin DV. Trofimov BA. Zh. Obshch. Khim.  1997,  67:  63 
    Google Scholar
  • 3a Bunlaksananusorn T. Knochel P. Tetrahedron Lett.  2002,  43:  5817 
    CrossrefGoogle Scholar
  • 3b Bookham JL. Smithies DM. J. Organomet. Chem.  1999,  577:  305 
    CrossrefGoogle Scholar
  • 4a

    See ref.2d

  • 4b Dombek BD. J. Org. Chem.  1978,  43:  3408 
    Google Scholar
  • 4c Wolfsberger W. Chem.-Ztg.  1988,  112:  53 
    Google Scholar
  • 5a Nagel U. Reigel B. Bublewitz A. J. Organomet. Chem.  1989,  370:  223 
    CrossrefGoogle Scholar
  • 5b Hoye PAT. Pringle PG. Smith MB. J. Chem. Soc., Chem. Commun.  1990,  1701 
    CrossrefGoogle Scholar
  • 5c Pringle PG. Brewin D. Smith MB. Worboys K. In Aqueous Organometallic Chemistry and Catalysis   Vol. 5:  Horvath IT. Joo F. Dordrecht; The Netherlands: 1995.  p.111 
    CrossrefGoogle Scholar
  • 5d Costa E. Pringle PG. Smith MB. Worboys K. J. Chem. Soc., Dalton Trans.  1997,  4277 
    CrossrefGoogle Scholar
  • 5e Wicht DK. Kourkine IV. Lew BM. Nthenge JM. Glueck DS. J. Am. Chem. Soc.  1997,  119:  5039 
    CrossrefGoogle Scholar
  • 5f Costa E. Pringle PG. Worboys K. Chem. Commun.  1998,  49 
    CrossrefGoogle Scholar
  • 5g Orpen AG. Pringle PG. Smith MB. Worboys K. J. Organomet. Chem.  1998,  550:  255 
    CrossrefGoogle Scholar
  • 5h Wicht DK. Kourkine IV. Kovacik I. Glueck DS. Concolino TE. Yap GPA. Incarvito CD. Rheingold AL. Organometallics  1999,  18:  5381 
    CrossrefGoogle Scholar
  • 5i Wicht DK. Kovacik I. Glueck DS. Liable-Sands LM. Incarvito CD. Rheingold AL. Organometallics  1999,  18:  5141 
    CrossrefGoogle Scholar
  • 5j Kovacik I. Wicht DK. Grewal NS. Glueck DS. Incarvito CD. Guzei IA. Rheingold AL. Organometallics  2000,  19:  950 
    CrossrefGoogle Scholar
  • 6a Takaki K. Takeda M. Koshoji G. Shishido T. Takehira K. Tetrahedron Lett.  2001,  42:  6357 
    CrossrefGoogle Scholar
  • 6b Douglass MR. Stern CL. Marks TJ. J. Am. Chem. Soc.  2001,  123:  10221 
    CrossrefGoogle Scholar
  • 6c Douglass MR. Marks TJ. J. Am. Chem. Soc.  2000,  122:  1824 
    CrossrefGoogle Scholar
  • 7 Shulyupin MO. Kazankova MA. Beletskaya IP. Org. Lett.  2002,  4:  761 
    CrossrefGoogle Scholar
  • 8 Schnyder A. Aemmer T. Indolese AF. Pittelkow U. Studer M. Adv. Synth. Catal.  2002,  244:  495 
    Google Scholar
  • 9 Kazankova MA. Efimova IV. Kochetkov AN. Afanas’ev VV. Beletskaya IP. Dixneuf PH. Synlett  2001,  497 
    Google Scholar
  • NiX2 or PdX2 (X = Cl, Br) react with diphenylphosphine under various conditions to form HX. See for example:
  • 10a Issleib K. Wenschuh E. Z. Anorg. Allg. Chem.  1960,  305:  15 
    CrossrefGoogle Scholar
  • 10b Hayter RG. Inorg. Chem.  1963,  2:  932 
    CrossrefGoogle Scholar
  • 10c Hayter RG. J. Am. Chem. Soc.  1962,  84:  3046 
    CrossrefGoogle Scholar
  • 10d Weston CW. Verstuyft AW. Nelson JH. Jonassen HB. Inorg. Chem.  1977,  16:  1313 
    CrossrefGoogle Scholar
  • 10e Weston CW. Bailey GW. Nelson JH. Jonassen HB. J. Inorg. Nucl. Chem.  1972,  34:  1752 
    CrossrefGoogle Scholar
  • 10f G iannandrea R. Mastrorilli P. Nobile C.-S. Dilonardo M. Inorg. Chim. Acta  1996,  249:  237 
    CrossrefGoogle Scholar
  • 11a Backvall JE. Bjorkman EE. J. Org. Chem.  1980,  45:  2893 
    CrossrefGoogle Scholar
  • 11b Hegedus LS. Akermark B. Zetterberg K. Olsson LF. J. Am. Chem. Soc.  1984,  106:  7122 
    CrossrefGoogle Scholar
  • 12a Petrov KA. Chauzov VA. Agafonov SV. Zh. Obshch. Khim.  1980,  50:  1510 
    Google Scholar
  • 12b Mironova ZN. Tzvetkov EN. Nikolaev AV. Kabachnik MI. Dyadin YuA. Zh. Obshch. Khim.  1974,  44:  1217 ; and references therein
    Google Scholar
  • 12c Legin GYa. Zh. Obshch. Chim.  1976,  46:  545 
    Google Scholar
  • 13a For review see: Clayden J. Warren S. Angew. Chem., Int. Ed. Engl.  1996,  35:  241 
    Google Scholar
  • 13b The synthesis of the pheromon of olive fly using 4f, see: Ley SV. Lygo B. Tetrahedron Lett.  1984,  24:  113 
    Google Scholar
  • 14a Artuhin PI. Shavinskiy BM. Mityakin YuL. Mironova ZN. Tzvetkov EN. Nikolaev AV. Kabachnik MI. Uzv. AN USSR, Ser. Khim.  1974,  41 
    Google Scholar
  • 14b Nikolaev AV. Durasov VB. Mironova ZN. Dokladi AN USSR  1969,  186:  603 
    Google Scholar
15

Experimental Conditions: In a 8 mm tube filled with argon were placed Ni(PPh3)2Br2 (55 mg, 5 mol%), Ph2PH (279 mg, 1,5 mmol), alkenyl ether (1.65 mmol) and dry benzene (3 mL). The tube was sealed and placed in a hot bath. Reaction time and temperature are given in Table [2] . After cooling the tube was opened and the solvent was evaporated. The residue was dissolved in 15 mL of Et2O and 2 ml 30% H2O2 was added. The mixture was stirred until the organic phase discoloured. The organic phase was separated, washed with water, dried under MgSO4 and evaporated in vacuum. The target compound was recrystallized from hexane or purified by column chromatography (Al2O3, Et2O). 1-Butoxy-ethyl(diphenyl)phosphine oxide (3a) was recrystallized from hexane (cooling up to -18 °C), colorless oil. 1H NMR (400 MHz, CDCl3): δ = 0.83-0.85 (t, 3 H), 1.22-1.26 (m, 2 H), 1.45-1.51 (m, 5 H), 3.19-3.25 (m, 1 H), 3.58-3.64 (m, 1 H), 4.19-4.23 (m, 1 H), 7.45-7.58 (m, 6 H), 7.88-7.92 (m, 2 H), 8.05-8.09 (m, 2 H). 31P{1H} NMR (162.6 MHz, CDCl3): δ = 30.0. Anal. Calcd: C, 71.52; H, 7.61. Found: C, 71.35; H, 7.45.