• Mild catalyst for the silylation of OH by silazanes: Tetrahedron Lett., 35, 8409 (1994), or by hydrosilanes and disilanes: Tetrahedron Lett., 35, 8413 (1994). See Appendix 4.
• Fluoride ion as a base in organic synthesis: Chem. Rev., 80, 429 (1980). Synthetic aspects of the use of organosilicon compounds under nucleophilic catalysis conditions: Tetrahedron, 44, 2675 (1988). For a brief feature on uses of TBAF, see: Synlett, 2125 (2002).
•
For the cleavage of disilanes to give "metal-free" silyl anions, see Hexamethyldisilane, A13155.• For nucleophilic displacement of halide or tosylate by TBAF in the preparation of alkyl and acyl fluorides, see: J. Org. Chem., 49, 3216 (1984); Org. Synth. Coll., 8, 258 (1993).
• Reagent for deprotection of N-Boc groups under mild conditions: Tetrahedron Lett., 43, 589 (2002).
• Many other examples exist where the reagent acts as a base in organic synthesis:
•
Ester enolates can be displaced from silicon, and trapped by reaction with carbonyl compounds without ɑ-hydrogens: Tetrahedron Lett., 1699 (1976). Under similar conditions, ketones with ɑ-hydrogens are converted under kinetic control to their silyl enol ethers with high (Z)-stereoselectivity (see Ethyl (trimethylsilyl)acetate, A17707): J. Am. Chem. Soc., 98, 2346 (1976); Org. Synth. Coll., 7, 512 (1990):
• Promotes the directed aldol condensation of silyl enol ethers with aldehydes at low temperatures under very mild conditions: J. Org. Chem., 48, 932 (1983); alkali metal fluorides give poor results.
• Reviews:
•
Specific reagent for the cleavage of silyl ethers, including TBDMS: J. Am. Chem. Soc., 94, 6190 (1972), (see tert-Butyldimethylchlorosilane, A13064), as well as the more stable TBDPS: Org. Synth. Coll., 9, 4 (1998), and TIPS: J. Org. Chem., 45, 4797 (1980); (see also tert-Butyldiphenylchlorosilane, A12721 and Chlorotriisopropylsilane, A17376).• Acylation of hindered OH groups: Tetrahedron Lett., 1691 (1977). Nitro-aldol formation from aldehydes and nitro compounds (Henry reaction) facilitated by high pressure: Angew. Chem. Int. Ed., 23, 617 (1984). Dieckmann-type cyclization of a diester: Org. Synth. Coll., 8, 71 (1993). Catalyzes the regioselective N-alkylation of silylated purines with chloromethyl ethers: Helv. Chim. Acta, 72, 1495 (1989).
Corrosive (C)
Flammable (F)
Harmful (X)
Toxic (T)
