The chemistry of tetramethyldisiloxane (TMDS) is largely composed of the reduction of functional groups with increasing applications for carboncarbon bond formation. This reagent can be a safe alternative to H 2 , LiAlH 4 , and other reactive reagents. Notable are the amide conversion to amines and aldehydes, nitro group reductions, nitrile reductions, hydrogenolysis of arylchlorine bonds, reductive formation of sulfides, reductive etherification, reductive opening of ketals, reductive demethoxylation, and formation of nitriles with homologation. Selectivity can be carried out by the choice of catalysts. This review of recent chemistry will focus on synthetically applied reactions of the recent past. Displayed reactions are chosen to be representative of the referenced work, but are also chosen to illustrate a new viewpoint. Finally, where applicable, the results of competing hydrosilanes are presented to compare to the results obtained with TMDS.

A general synthetic method for the Hofmann rearrangement of protected asparagines has been developed. Reaction of asparagine derivatives with iodosobenzene diacetate (PIDA) in mixed solvents produces β-amino-l-alanines in good yield. Advantages over the commonly used reagent bis(trifluoroacetoxy)iodobenzene have been discussed.

The β-amino alcohol 4β-morpholinocaran-3α-ol is prepared by addition of morpholine to α-3,4-epoxycarane utilizing anhydrous magnesium bromide as Lewis acid promoter. The enantiopure amino alcohol is uniquely effective as a chiral moderator for the addition of lithium cyclopropylacetylide to an unprotected N-acylketimine. This reaction provides an efficient route to the second generation NNRTI drug candidate DPC 963.

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