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18.11.3.1.4 Method 4: Substitution Reactions with Sodium Hydrogen Selenide or Hydrogen Selenide

DOI: 10.1055/sos-SD-018-01081

Schmidt, J.; Silks, L. A.Science of Synthesis, (200518980.

A commonly used method for the installation of the selenocarbonyl group within a heteroatom framework involves the substitution reaction of an activated precursor with hydrogen selenide or sodium hydrogen selenide. As shown in Scheme 14, the thiocarbonyl group in 31 serves as a key functional group capable of reacting with a variety of electrophiles ultimately giving rise to a leaving group by sulfur alkylation.[‌47‌] In this example, the alkylation process using triethyl orthoformate in the presence of boron trifluoridediethyl ether complex effectively transfers an ethyl group to the thiocarbonyl sulfur of 31. The resulting iminium group of 32 activates the quaternary carbon for attack by the nucleophilic sodium hydrogen selenide species, giving rise to an intermediate tetrahedral species which can collapse to expel ethanethiolate to afford the selenocarbonyl compound 33 (Scheme 14).[‌47‌‌50‌]

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