21 July 2011 (online)
1,1,3,3-Tetramethyldisiloxane (TMDS) is a hydrosiloxane derivative and has been used in organic synthesis as a mild reducing agent and intermediate for the preparation of organopolysiloxanes. It is a rather cheap, little hazardous, safe, volatile liquid boiling at 71 ˚C and is stable towards air and moisture. [¹] It has been used as a reducing agent for the direct synthesis of alkyl halides from aldehydes [²] and for the synthesis of alkyl halides from epoxides. [³] It was also found to be a mild donor of hydride for selective semihydrogenation of acetylenes to olefins,  it is used for the reduction of aryl chlorides to the corresponding arenes,  the reduction of unsymmetrical secondary phosphine oxides to secondary phosphine,  the reductive cleavage of inert C-O bonds,  and the preparation of aldenamines from carboxamides.  The enantioselective reductive Michael cyclization of substrates containing two α,β-unsaturated carbonyl moieties has been achieved by the use of a combination of TMDS and chiral copper-bisphosphine complexes.  Reduction and reductive N-alkylation of secondary amides to secondary amines with a ruthenium complex/TMDS system are readily accomplished. [¹0]
1,1,3,3-Tetramethyldisiloxane is a by-product of the silicon industry and the lowest-molecular-weight commercially available hydrosiloxane derivative now. It can be readily prepared by reduction of 1,1,3,3-tetramethyl-1,3-dichloro-1,3-disiloxane with a metal hydride such as lithium aluminum hydride, sodium aluminum hydride, lithium borohydride, lithium hydride or sodium hydride in tetrahydrofuran.
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