New Syntheses of Bismuthonium Salts, Bismuthonium Ylides and Bismuthane Imides Using Triarylbismuth(V)-Oxo and -Hydroxo Compounds

Abstract

Triarylbismuth(V)-oxo and -hydroxo compounds react with organoboronic acids and esters in the presence of BF₃·OEt₂ to afford the corresponding bismuthonium salts. They also undergo dehydrative coupling with cyclic 1,3-dicarbonyl compounds, amides and sulfonamides to give stabilized bismuthonium ylides, bismuthane N-acylimides and bismuthane N-sulfonylimides, respectively. All reactions proceed efficiently under mild conditions.

bismuthane oxides - bismuthonium salts - bismuthonium ylides - bismuthane imides

References

<A NAME="RF00102SS-1A">1a</A> Barton DHR. Finet J.-P. Pure Appl. Chem.  1987,  59:  937 

<A NAME="RF00102SS-1B">1b</A> Abramovitch RA. Barton DHR. Finet J.-P. Tetrahedron  1988,  44:  3039 

<A NAME="RF00102SS-1C">1c</A> Finet J.-P. Chem. Rev.  1989,  89:  1487 

<A NAME="RF00102SS-2A">2a</A> Freedman LD. Doak GO. Chem. Rev.  1982,  82:  15 

<A NAME="RF00102SS-2B">2b</A> Lloyd D. Gosney I. In The Chemistry of Organic Arsenic, Antimony and Bismuth Compounds   Chap. 16:  Patai S. Wiley; New York: 1994.  p.657-693  

<A NAME="RF00102SS-2C">2c</A> Matano Y. Suzuki H. Bull. Chem. Soc. Jpn.  1996,  69:  2673 

<A NAME="RF00102SS-2D">2d</A> Suzuki H. Ikegami T. Matano Y. Synthesis  1997,  249 

<A NAME="RF00102SS-2E">2e</A> Matano Y. Ikegami T. In Organobismuth Chemistry   Chap. 3:  Suzuki H. Matano Y. Elsevier; New York: 2001.  p.249-327  

<A NAME="RF00102SS-2F">2f</A> Komatsu N. In Organobismuth Chemistry   Chap. 5:  Suzuki H. Matano Y. Elsevier; New York: 2001.  p.371-440  

<A NAME="RF00102SS-2G">2g</A> Elliott GI. Konopelski JP. Tetrahedron  2001,  57:  5683 

<A NAME="RF00102SS-3A">3a</A> Barton DHR. Charpiot B. Motherwell WB. Tetrahedron Lett.  1982,  23:  3365 

<A NAME="RF00102SS-3B">3b</A> Matano Y. Azuma N. Suzuki H. J. Chem. Soc., Perkin Trans. 1  1994,  1739 

<A NAME="RF00102SS-3C">3c</A> Matano Y. Yoshimune M. Suzuki H. Tetrahedron Lett.  1995,  36:  7475 

<A NAME="RF00102SS-3D">3d</A> Matano Y. Yoshimune M. Azuma N. Suzuki H. J. Chem. Soc., Perkin Trans. 1  1996,  1971 

<A NAME="RF00102SS-3E">3e</A> Matano Y. Organometallics  2000,  19:  2258 

<A NAME="RF00102SS-3F">3f</A> Matano Y. Chem. Commun.  2000,  2233 

<A NAME="RF00102SS-4A">4a</A> Glidewell C. Lloyd D. Metcalfe S. Synthesis  1988,  319 

<A NAME="RF00102SS-4B">4b</A> Ogawa T. Murafuji T. Suzuki H. Chem. Lett.  1988,  849 

<A NAME="RF00102SS-4C">4c</A> Ogawa T. Murafuji T. Iwata K. Suzuki H. Chem. Lett.  1989,  325 

<A NAME="RF00102SS-4D">4d</A> Kirij NV. Pasenok SV. Yagupolskii YL. Naumann D. Tyrra W. J. Fluorine Chem.  1994,  66:  75 

<A NAME="RF00102SS-4E">4e</A> Matano Y. J. Chem. Soc., Perkin Trans. 1  1994,  2703 

<A NAME="RF00102SS-4F">4f</A> Matano Y. Yoshimune M. Suzuki H. J. Org. Chem.  1995,  60:  4663 

<A NAME="RF00102SS-4G">4g</A> Rahman MM. Matano Y. Suzuki H. J. Chem. Soc., Perkin Trans. 1  1999,  1533 

<A NAME="RF00102SS-5A">5a</A> Wittig G. Hellwinkel D. Chem. Ber.  1964,  97:  789 

<A NAME="RF00102SS-5B">5b</A> Suzuki H. Nakaya C. Matano Y. Ogawa T. Chem. Lett.  1991,  105 

<A NAME="RF00102SS-5C">5c</A> Pasenok SV. Kirij NV. Yagupolskii YL. Naumann D. Tyrra W. J. Fluorine Chem.  1993,  63:  179 

<A NAME="RF00102SS-5D">5d</A> Suzuki H. Ikegami T. J. Chem. Res. (S)  1996,  24 

<A NAME="RF00102SS-5E">5e</A> Ikegami T. Suzuki H. Organometallics  1998,  17:  1013 

<A NAME="RF00102SS-5F">5f</A> Matano Y. Nomura H. Suzuki H. J. Organomet. Chem.  2000,  611:  89 

<A NAME="RF00102SS-5G">5g</A> Matano Y. Nomura H. Suzuki H. Shiro M. Nakano H. J. Am. Chem. Soc.  2001,  123:  10954 

<A NAME="RF00102SS-5H">5h</A> Nitta M. Mitsumoto Y. Yamamoto H. J. Chem. Soc., Perkin Trans. 1  2001,  1901 

<A NAME="RF00102SS-6">6</A> Matano Y. Nomura H. J. Am. Chem. Soc.  2001,  123:  6443 

<A NAME="RF00102SS-7">7</A>

When dried in vacuo for several hours, 2a was dehydrated to give a polymeric triphenylbismuthane oxide as an amorphous powder. See Ref. [6]

<A NAME="RF00102SS-8A">8a</A> Matano Y. Begum SA. Miyamatsu T. Suzuki H. Organometallics  1998,  17:  4332 

<A NAME="RF00102SS-8B">8b</A> Matano Y. Begum SA. Miyamatsu T. Suzuki H. Organometallics  1999,  18:  5668 

<A NAME="RF00102SS-9A">9a</A> Barton DHR. Blazejewski J.-C. Charpiot B. Finet J.-P. Motherwell WB. Papoula MTB. Stanforth SP. J. Chem. Soc., Perkin Trans. 1  1985,  2667 

<A NAME="RF00102SS-9B">9b</A> Suzuki H. Murafuji T. Ogawa T. Chem. Lett.  1988,  847 

<A NAME="RF00102SS-10">10</A> Ogawa et al. prepared 6a in 84% yield by the reaction of Ph₃BiO with a sodium salt of 5a. Ogawa T. Murafuji T. Suzuki H. J. Chem. Soc., Chem. Commun.  1989,  1749 ; they also obtained 6a in 52% yield by the successive treatment of 5a with two equivalents of NaH and 1a in THF

<A NAME="RF00102SS-11">11</A>

Matano, Y.; Nomura, H.; Suzuki, H. Inorg. Chem., in press.

<A NAME="RF00102SS-12">12</A>

In this reaction, triarylbismuthane and aniline were obtained in good yields. This result suggested that the initially formed triarylbismuthane N-benzoylimide would thermally decompose to generate the bismuthane and phenyl isocyanate. See Ref. [5g]