Abstract
This chapter discusses the different methods for synthesis of phosphaalkynes and arsaalkynes and covers the literature from 1995 to 2003. Elimination and rearrangement reactions are the most important methods for phosphaalkyne synthesis. The most frequently employed method for the preparation of kinetically stabilized phosphaalkynes is the elimination of hexamethyldisiloxane from readily available phosphaalkenes. This protocol was first described in 1981 by Becker and was optimized and generalized by Regitz in 1986. A further important method was described by Denis who prepared substituted phosphaalkynes by elimination of HCl from α-dichlorophosphines. The base-induced elimination at low temperature or the vacuum gas–solid reaction (VGSR) are the most efficient protocols for this synthetic method. Only very few examples of arsaalkynes are described and covered in Section 5.31.2.
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