AbstractThe 1‐heteroalkylation of the tris‐(trimethylsilyl)phosphine was thoroughly investigated using heterosubstituted methylamines, chloromethyl alkyl ethers, methyl chloroformate, paraformaldehyde, and dialkylformamides. Convenient methods for the synthesis of tris(dialkylaminomethyl)phosphines, tris(alkoxymethyl)phosphines, tris(methoxycarbonyl) phosphine, and several phosphaethylenes were proposed on the basis of the 1‐heteroalkylation of tris(trimethylsilyl)phosphine as a valuable synthon. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:441–445, 2010; View this article online at wileyonlinelibrary.com. DOI 10.1002/hc.20636