The preparation of three new partially deuterated hexadecanethiols for applications in surface chemistry

The synthesis of three partially deuterated hexadecanethiols has been achieved. Thiols CH 3 (CH 2 ) 7 (CD 2 ) 8 SH, CD 3 (CD 2 ) 7 (CH 2 ) 8 SH and CD 3 (CH 2 ) 15 SH were targeted, as these compounds, after formation of self‐assembled monolayers on Au(1 1 1) or Au nanoparticles, can provide mechanistic information pertaining to reactive atom migrations within the assembly. The syntheses of each of these compounds called upon Grignard coupling chemistry, which was activated by Li 2 CuCl 4 . Applicable deuterium containing fragments were either commercially obtained or constructed from by way of an inexpensive and efficient ring opening, protection and dimerization of THF‐ d 8 . Sulfur incorporation was by thiolacetate substitution or addition reactions. The protocols presented possess general applicability in a number of syntheses requiring block‐deuterated fattyalkyl sections. Copyright © 2008 John Wiley & Sons, Ltd.