Like the preceding method, the most popular method for synthesizing phosphaalkynes is reliant upon the expulsion of products containing strong silicon-element bonds. Specifically, it is possible to synthesize phosphaalkynes via the elimination of hexamethyldisiloxane (HMDSO) from certain silylated phosphaalkenes with the general structure RO(SiMe)C=PSiMe. These phosphaalkenes are formed rapidly following the synthesis of the appropriate acyl bis-trimethylsilylphosphine, which undergoes a rapid [1,3]-silyl shift to produce the relevant phosphaalkene. This synthetic strategy is particularly appealing because the precursors (an acyl chloride and tris-trimethylsilylphosphine or bis-trimethylsilylphosphide) are either readily available or simple to synthesize.
This method has been utilized to produce a variety of kinetically stable phosphaalkynes, including aryl, tertiary alkyl, secondary alkyl, and even primary alkyl phosphaalkynes in good yields.