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Synthesis 2011(24): 4091-4098  
DOI: 10.1055/s-0031-1289612
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Electroreduction of Triphenylphosphine Oxide to Triphenylphosphine in the Presence of Chlorotrimethylsilane

Hiromu Kawakuboa, Manabu Kuroboshi*b, Tomotake Yanob, Kazuma Kobayashib, Syogo Kamenoueb, Tomomi Akagib, Hideo Tanaka*b
a API Department, Asahi Kasei Chemicals Corporation, Kanda Jinbocho 1-105, Chiyoda-ku, Tokyo 101-8101, Japan
b The Graduate School of Natural Science and Technology, Okayama University, Tsushima-Naka 3-1-1, Okayama 700-8530, Japan
Fax: +81(86)2518079; e-Mail: tanaka95@cc.okayama-u.ac.jp;
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Publication History

Received 11 August 2011
Publication Date:
18 November 2011 (online)

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Abstract

Electroreduction of triphenylphosphine oxide to triphenylphosphine in an acetonitrile solution of tetrabutylammonium bromide in the presence of chlorotrimethylsilane was performed successfully in an undivided cell fitted with a zinc anode and a platinum cathode under constant current. A plausible mechanism involving, (1) one-electron reduction of triphenylphosphine oxide generating the corresponding anion radical [Ph3P˙ -O-], (2) subsequent reaction with chlorotrimethylsilane affording the (trimethylsiloxy)triphenylphosphorus radical [Ph3P˙ -OSiMe3], and (3) further one-electron reduction followed by P-O bond fission leading to triphenylphosphine is proposed. In a similar manner, electroreduction of some triarylphosphine oxides and alkyldiarylphosphine oxides was executed to give the corresponding phosphine derivatives in good to moderate yields.

Key words

reduction - electron transfer - phosphorus - silicon

    References

  • 1a Maercker A. In Organic Reactions   Vol. 14:  John Wiley & Sons; New York: 1965.  Chap. 3.
    Google Scholar
  • 1b Boutagy J. Thomas R. Chem. Rev.  1974,  74:  87 
    Google Scholar
  • 2a Hughes DL. In Organic Reactions   Vol. 42:  John Wiley & Sons; New York: 1992.  Chap. 2.
    Google Scholar
  • 2b Mitsunobu O. Yamada M. Bull. Chem. Soc. Jpn.  1967,  40:  2380 
    Google Scholar
  • 2c Mukaiyama T. Matsueda R. Maruyama H. Bull. Chem. Soc. Jpn.  1970,  43:  1271 
    Google Scholar
  • 3a Mukaiyama T. Araki M. Takei H. J. Am. Chem. Soc.  1973,  95:  4763 
    Google Scholar
  • 3b Corey EJ. Nicolaou KC. J. Am. Chem. Soc.  1974,  96:  5614 
    Google Scholar
  • 3c Corey EJ. Nicolaou KC. Melvin LS. J. Am. Chem. Soc.  1975,  97:  653 
    Google Scholar
  • 3d Modification: Gerlach H. Thalmann A. Helv. Chim. Acta  1974,  57:  2661 
    Google Scholar
  • 4a Appel R. Angew. Chem., Int. Ed. Engl.  1975,  14:  801 
    Google Scholar
  • 4b Calzada JG. Hooz J. Org. Synth.  1974,  54:  63 
    Google Scholar
  • 5a Staudinger H. Meyer J. Helv. Chim. Acta  1919,  2:  635 
    Google Scholar
  • 5b Gololobov YG. Zhmurova IN. Kasukhin LF. Tetrahedron  1981,  37:  437 
    Google Scholar
  • 5c Scriven EFV. Turnbull K. Chem. Rev.  1988,  88:  297 
    Google Scholar
  • 5d Gololobov YG. Kasukhin LF. Tetrahedron  1992,  48:  1353 
    Google Scholar
  • 5e Shah S. Protasiewicz JD. Coord. Chem. Rev.  2000,  210:  181 
    Google Scholar
  • 6 Phosphorus is obtained economically from limited regions of the world: Kuroda A. Takiguchi N. Kato J. Ohtake H. J. Environ. Biotech.  2005,  4:  87 
    Google Scholar
  • 7 As an another approach, catalytic Wittig reaction using 3-methyl-1-phenylphospholane 1-oxide was reported: O’Brien CJ. Tellez JL. Nixon ZS. Kang LJ. Carter AL. Kunkel SR. Przeworski KC. Chass GA. Angew. Chem. Int. Ed.  2009,  48:  6836 
    Google Scholar
  • 8a Fritzsche H. Chem. Ber.  1965,  98:  171 
    Google Scholar
  • 8b Coumbe T. Lawrence NJ. Muhammad F. Tetrahedron Lett.  1994,  35:  625 
    Google Scholar
  • 8c Marsi FM. J. Org. Chem.  1974,  39:  265 
    Google Scholar
  • 9a Horner L. Hoffmann H. Beck P. Chem. Ber.  1958,  91:  1583 
    Google Scholar
  • 9b Imamoto T. Tanaka T. Kusumoto T. Chem. Lett.  1985,  14:  1491 
    Google Scholar
  • 9c Griffin S. Heath L. Wyatt P. Tetrahedron Lett.  1998,  39:  4405 
    Google Scholar
  • 9d Nelson GE. inventors; US  4,507,502.  ; Chem. Abstr. 1985, 103, 37617
  • 9e Busacca CA. Raju R. Grinberg N. Haddad N. James-Jones P. Lee H. Lorenz JC. Saha A. Senanayake CH. J. Org. Chem.  2008,  73:  1524 
    Google Scholar
  • 9f Malpass DB, and Yeargin GS. inventors; US  4,113,783.  ; Chem. Abstr. 1979, 90, 23256
  • 10 Handa Y. Inanaga J. Yamaguchi M. J. Chem. Soc., Chem. Commun.  1989,  298 
    Google Scholar
  • 11 Mathey F. Maillet R. Tetrahedron Lett.  1980,  21:  2525 
    Google Scholar
  • 12 Dockner T. Angew. Chem.  1988,  100:  699 
    Google Scholar
  • 13 Timokhin BV. Kazantseva MV. Blazhev DG. Rokhin AV. Russ. J. Gen. Chem.  2000,  70:  1310 ; Chem. Abstr. 2001, 134, 311265
    Google Scholar
  • 14a Iorga B. Camichael D. Savignac P. C. R. Acad. Sci., Ser. IIC  2000,  3:  821 
    Google Scholar
  • 14b Hermeling D, Hugo R, Lechtken P, Rotermund GW, and Siegel H. inventors; DE  19,532,310.  ; Chem. Abstr. 1997, 126, 199670
  • 14c Masaki M. Fukui K. Chem. Lett.  1977,  6:  151 
    Google Scholar
  • Triphenylphosphorus dichloride (3a) is also prepared by treatment of 2 with chlorinating reagents such as diphosgene, triphosgene, and phosphorus pentachloride.
  • 15a Rao VJ, and Reddy AM. inventors; IN  1996-DE1812.  ; Chem. Abstr. 2007, 146, 402090
    Google Scholar
  • 15b Li H, Chen Z, Wu L, Wang C, and Hu B. inventors; CN  1,660,862.  ; Chem. Abstr. 2006, 144, 488805
    Google Scholar
  • 15c Horner L. Hoffmann H. Beck P. Chem. Ber.  1958,  91:  1583 
    Google Scholar
  • 16 Theoretical calculation: Mo O. Eckert-Maksic YM. Maksic ZB. Alkorta I. Elguero J. J. Phys. Chem. A.  2005,  109:  4359 
    Google Scholar
  • 17 Masaki M, and Kaketani N. inventors; JP  53-034,725.  ; Chem. Abstr. 1978, 89, 109953
  • 18 Fukui K, Kaketani N, Kita J, and Fujimura S. inventors; JP  55-149,293.  ; Chem. Abstr. 1981, 94, 175259
  • 19 Horner L. Beck P. Hoffmann H. Chem. Ber.  1959,  92:  2088 
    Google Scholar
  • 20 Hermeling D, Siegel H, Hugo R, and Rotermund GW. inventors; EP  725,073.  ; Chem. Abstr. 1996, 125, 195993
  • 21 Wettling T. inventors; EP  5,48,682.  ; Chem. Abstr. 1993, 119, 139547
  • 22 Young DA, and Brannock KC. inventors; US  3,780,111.  ; Chem. Abstr. 1974, 80, 60039
  • 23a Organic Electrochemistry   4th ed.:  Lund H. Hammerich O. Marcel Dekker; New York: 1991. 
    Google Scholar
  • 23b Torii S. In Electroorganic Reduction Synthesis   Kodansha & Wiley-VCH; Tokyo/Weinheim: 2006. 
    Google Scholar
  • 23c New Developments in Organic Electrosynthesis   Fuchigami T. CMC; Tokyo: 2004. 
    Google Scholar
  • 23d Electroorganic Chemistry, Kagaku Zokan   Vol. 86:  Osa T. Shono T. Honda K. Kagaku Dojin; Kyoto: 1980. 
    Google Scholar
  • 24a Santhanam KSV. Bard AJ. J. Am. Chem. Soc.  1968,  90:  1118 
    Google Scholar
  • 24b Raju T, Kulangiappar K, Kulandainathan MA, Muthukumaran A, and Krishnan V. inventors; IN  2002-DE793.  ; Chem. Abstr. 2007, 147, 235305
  • 25 CRC Handbook of Chemistry & Physics   74th ed.:  Lide DR. CRC Press; London: 1993. 
    Google Scholar
  • 27 Yano T. Hoshino M. Kuroboshi M. Tanaka H. Synlett  2010,  801 
    Google Scholar
  • 28 Yano T. Kuroboshi M. Tanaka H. Tetrahedron Lett.  2010,  51:  698 
    Google Scholar
  • 29 Kuroboshi M. Yano T. Kamenoue S. Kawakubo H. Tanaka H. Tetrahedron  2011,  67:  5825 
    Google Scholar
  • 30 Tanaka H. Yano T. Kobayashi K. Kamenoue S. Kuroboshi M. Kawakubo H. Synlett  2011,  582 
    Google Scholar
26

Since 3a is highly moisture sensitive, 3a was used without purification.

31

Among thus far examined solvents, MeCN was the only solvent effective for the present purpose; thus, electro-reduction of 2a to 1a hardly occurred in THF, DMSO, DMF, and 1,4-dioxane. The electroreduction proceeded in a mixture of THF and MeCN (4:1 to 1:4).

32

As a supporting electrolyte, Bu4NOTf, Bu4NBF4, and Bu4NClO4 could be used to give 1a in slightly lower yields (42, 38, and 52%, respectively). The electroreduction of 2a proceeded without supporting electrolyte to give 1a in 41% yield.

33

One singlet signal appeared at δ = 32.5 ppm in the ³¹P NMR of a mixture of 2a, Me3SiCl, and Bu4NBr. On the other hand, a mixture of 2a and Me3SiBr showed a singlet peak at δ = 48.7 ppm. These results suggest that Me3SiCl would react partially with Bu4NBr to give Me3SiBr, which would inter-act with 1a to form a trace amount of [Ph3P+-O-SiMe3]Br-. However, since the electroreduction of Ph3P=O (2a) proceeded without Br- source (ref. 32), the electroreduction of 2a seems to proceed mainly through the ECEC mechanism (Scheme  [6] ).