{uni_hamburg} Short: II/25D

{ALF} Can also function as a protected form of ammonia, e.g. to convert acid chlorides to primary amides: Synthesis, 517 (1985), and substituted maleic anhydrides to maleimides: Tetrahedron Lett., 31, 5201 (1990).

{ALF} For conversion of carbonyl groups to silyl enol ethers, see Iodotrimethyl­silane, A12902.

{ALF} Convenient, mild silylating reagent which generates gaseous ammonia as the only by-product (see Appendix 4). Non-acidic substrates normally require a catalyst.

{ALF} A range of catalysts for silylation with HMDS, including saccharin and sodium saccharin, has been recommended: J. Org. Chem., 47, 3966 (1982), for silylation of alcohols, phenols, thiols, carboxylic acids, amides, thioamides, hydroxamic acids, hydrazides, NH-groups of heterocycles, hydrazines, 1,3-diketones, etc. The use of TBAF (0.02 eq.) or iodine (0.01 eq.) also provide mild procedures for O-silylation: Tetrahedron Lett., 35, 8409 (1994); J. Org. Chem., 65, 7228 (2000).

{ALD} Merck: 14,4689

Beilstein: 4,IV,4014

{uni_hamburg} Short: III/35B

{ALF} Silylation of alcohols, including carbohydrates, is catalyzed by TMS chloride: J. Org. Chem., 23, 50 (1958); J. Am. Chem. Soc., 85, 2497 (1963); Chem. Ind. (London), 794 (1984). Silylation of phenols occurs readily, see also: Liebigs Ann. Chem., 20 (1973).

{ALF} The Na, Li and K derivatives are useful strong bases; see Sodium bis(trimethyl­silyl)­amide, L13352, Lithium bis(trimethyl­silyl)­amide, L15012, and Potassium bis(trimethyl­silyl)­amide, L15022.

{ALF} HMDS in the presence of TMS chloride permits the selective O-silylation of amino alcohols: Synthesis, 990 (1988). Alcohols and phenols can be silylated in the presence of amines and thiols with ZnCl2 as catalyst: Synth. Commun., 23, 1633 (1993).

{ALF} In combination with DMSO, thiols are oxidized to disulfides under nearly neutral conditions: Synlett, 346 (2002).

{ALD} Merck: 14,4689