Organoselenium chemistry

For reviews of sulfur-containing carbanions, see Oae, S. Uchida, Y. in Patai Rappoport Stirling The Chemistry ofSulphones and Sulphoxides, Wiley NY, 1988, p. 583 Wolfe, S. in Bemardi Csizmadia Mangini Organic Sulfur Chemistry Elsevier, NY, 1985, p. 133 Block, E. Reactions ofOrganosulfur Compounds Academic Press NY, 1978, p. 42 Durst, T. Viau, R. Intra-Sci. Chem. Rep., 1973, 7 (3), 63. For a review of selenium-stabilized carbanions, see Reich, H.J. in Liotta Organoselenium Chemistry Wiley NY, 1987, p. 243. For support for this theory, see Wolfe, S. LaJohn, L.A. Bemardi, F Mangini, A. Tonachini, G. Tetrahedron Lett., 1983, 24, 3789 Wolfe, S. Stolow, A. LaJohn, L.A. Tetrahedron Lett., 1983, 24, 4071. 

For reviews of selenylations, see Back, T.G. in Liotta Organoselenium Chemistry, Wiley NY, 1987, p. 1 Paulmier, C. Selenium Reagents and Intermediates in Organic Synthesis Pergamon Elmsford, NY, 1986, p. 95. 

Scheme 56 summarizes Mori s synthesis of (S)-vesperal (38), the female sex pheromone of the longhorn beetle (Vesperus xatarti) [85]. (F)-Limonene yielded (S)-38 by utilizing organoselenium chemistry. 

T.G. Back Organoselenium Chemistry, Oxford University Press, Oxford, 1999. 

T. Murai and S. Kato, in Organoselenium Chemistry Topics in Current Chemistry 208, Springer, Berlin, 2000, 177. 

F. Ogura and K. Takamiya in "Organoselenium Chemistry", ed. T. G. Bock, Oxford University Press, Oxford, 1999, p. 257. 

Although over a quarter of a century ago it would not have been predicted that the importance of the VIA family of the periodic table would exceed that of its second element, sulphur, the development of organoselenium chemistry has been so explosive that little comment is necessary, as illustrated by the impressive number of papers as well as by several books on the field. Tellurium compounds have taken an even longer time to rise from being considered an exotic and perverse element to a useful tool in organic chemistry. 

D. Liotta, ed., Organoselenium Chemistry, John Wiley Sons, New York, 1987. 

See, for example, Baldwin Brown Ho He J. Am. Chem. Soc. 1971,93, 788 Yamamoto Oda Inouye J. Chem. Soc., Chem. Commun. 1973,848 Ranganathan Ranganathan Sidhu Mehrotra Tetrahedron Lett. 1973,3577 Murata Nakai Chem. Lett. 1990, 2069. For reviews with respect to selenium compounds, see Reich, in Liotta Organoselenium Chemistry, Wiley. New York, 1987, pp. 365-393 Reich, in Trahanovsky Oxidation in Organic Chemistry, pt. C Academic Press New York, 1978, pp. 102-111. 

This chapter concentrates on the developments in organoselenium chemistry from 1993 to 2004 and is therefore a continuation and extention of the chapter Selenium by Krief in the previous edition of Comprehensive Organometallic Chemistry,18 During that period many aspects of organoselenium chemistry have been covered in review articles19-35 and in books completely devoted to different areas of selenium.36-40 These reports highlight the current activities in selenium chemistry and stress the importance of selenium-containing molecules in different areas. 

As already mentioned, the ry -elimination of selenoxides was discovered around 197010 and had a major impact on the development of organoselenium chemistry. This reaction is about three orders of magnitude more rapid than the elimination of the corresponding less polar and less basic sulfoxides. Sigmatropic rearrangements proceed at markedly lower temperatures. These reactions are discussed in detail in Section 9.11.2.5. 

Krief, A. Hevesi, L. Organoselenium Chemistry I - Functional Group Transformations, Springer Heidelberg, 1988. 

Beaulieu, P. L. Deziel, R. In Organoselenium Chemistry A Practical Approach-, Back, T. G., Ed. Oxford University Press Oxford, 1999 pp 35-66. 

Iwaoka, M. Tomoda, S. In Organoselenium Chemistry Modem Developments in Organic Synthesis, Wirth, T., Ed. Topics in Current Chemistry 208 Springer Berlin, 2000 pp 55-80. 

Though you have only seen a couple of examples of the latter, it is clear that organosulfur and organoselenium chemistry are closely related. In the next chapter we will look at the quite different type of chemistry exhibited by organic compounds containing three other heteroatoms—silicon, tin, and boron. 

---