1,1,3,3-Tetramethyldisiloxane

Introduction

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, [4] it is used for the reduction of aryl chlorides to the corresponding arenes, [5] the reduction of unsymmetrical secondary phosphine oxides to secondary phosphine, [6] the reductive cleavage of inert C-O bonds, [7] and the preparation of aldenamines from carboxamides. [8] 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. [9] 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.

Scheme 1

References

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