Tri-n-butyltin hydride

• Catalog No.: A13298
• CAS Number: 688-73-3
• M. F.: C12H27Sn
• M. W.: 290.04378
• Purity: 97%

SYNONYMS

• Title: 三正丁基氢化锡
• IUPAC name: tributylstannane
• IUPAC Traditional name: tributyltin
• Synonyms: Tri-n-butylstannane; TBTH

DATABASE IDS

• Beilstein Number: 3587329
• EC Number: 211-704-4
• CAS Number: 688-73-3
• MDL Number: MFCD00009416

PROPERTIES

• Purity: 97%
• Boiling Point: 68-74°C/0.3mm
• Density: 1.098
• Flash Point: 40°C(104°F)
• Melting Point: 0-1°C
• Refractive Index: 1.4730
• GHS Hazard statements: H301-H312-H315-H319-H372-H226-H400-H410
• European Hazard Symbols: Toxic (T)
• European Hazard Symbols: Nature polluting (N)
• GHS Precautionary statements: P280-P273-P305+P351+P338-P309-P310-P501A
• Risk Statements: 10-21-25-36/38-48/23/25-50/53
• RTECS: WH8675000
• Safety Statements: 36/37/39-45-60-61
• Storage Warning: Air & Moisture Sensitive
• TSCA Listed: 是
• Hazard Class: 6.1
• UN Number: UN2929
• Packing Group: II

REFERENCES

• Reducing agent and source of tributyltin radicals. Widely used for selective reduction of alkyl halides to alkanes by a radical chain mechanism. The reaction is tolerant of a wide range of functionality, including OH and NH, in contrast to polar metal hydride reagents. For reviews, see: Synthesis, 499 (1970); 665 (1987). For a brief feature on uses of this reagent in synthesis, see: Synlett, 173 (2007). For use in the synthesis of deoxy sugars via reductive rearrangement of glycosyl bromides, see: Org. Synth. Coll., 8,583 (1993). Cyclization of the initially-formed alkyl radical to a suitably positioned double bond may occur. Formation of 5-membered rings is strongly favoured, and ring closure onto an existing ring gives the cis-fused product. See, e.g.: J. Am. Chem. Soc., 108, 5893 (1986):
  
• Intermolecular coupling with electron-deficient alkenes is also effective: Angew. Chem. Int. Ed., 23, 69 (1984); Org. Synth. Coll., 8, 148 (1993). Review: Synthesis, 417 (1988).
• Secondary alcohols can be deoxygenated by reduction of their xanthate derivatives: J. Chem. Soc., Perkin 1, 1574 (1975); Org. Synth. Coll., 7, 139 (1990), avoiding the rearrangements encountered with carbocation-based methods.
• TBTH also cleaves other C-heteroatom bonds, controlled by the stability of the resulting radical: Nitro-groups at tertiary centers are readily cleaved: Synthesis, 693 (1986). Azides are readily reduced to amines: Synlett, 342 (1991). C-S and C-Se bonds are also cleaved. J. Am. Chem. Soc., 104, 2046 (1982); 112, 4008 (1990); J. Org. Chem., 49, 5206 (1984); 54, 1234 (1989).
• Dialdehydes and keto aldehydes undergo free-radical intramolecular pinacol coupling to give cyclic diols: J. Am. Chem. Soc., 117, 7283 (1995); J. Org. Chem., 63, 6357 (1998).
• For generation and use of tributylstannyllithium, see: Org. Synth. Coll., 8, 562 (1993). Hydroxymethylation of TBTH occurs with LDA and paraformaldehyde. Subsequent reaction with dimethoxymethane gives the hydroxymethyl anion equivalent tributyl[(methoxymethoxy)methyl]stannane: Org. Synth. Coll., 9, 493, 704 (1998).
• Arylstannanes have been produced by Pd-catalyzed coupling with aryl iodides: Synlett, 1064 (2000).
• Free-radical hydrostannylation of alkenes occurs with TBTH to give alkylstannanes. The reaction is catalyzed by, e.g. Rh complexes: Chem. Lett., 881 (1988), or Pd complexes: Angew. Chem. Int. Ed., 35, 1329 (1996), and refs therein. Syn-addition to alkynes gives vinylstannanes, useful intermediates which undergo electrophilic substitution reactions with retention of configuration. Thus, iodine, NIS and NBS give vinyl halides: J. Org. Chem., 47, 404 (1982); Tetrahedron, 42, 3575 (1986), and alkyllithium compounds exchange to give vinyllithiums: J. Am. Chem. Soc., 99, 7365 (1977). Intramolecular reaction with a double bond has been used in cyclization reactions: Org. Synth. Coll., 8, 381 (1993):