4‐Trimethylsilyl‐3‐butyn‐2‐ol

[6999-19-5] C7H14OSi (MW 142.27) InChI = 1S/C7H14OSi/c1-7(8)5-6-9(2,3)4/h7-8H,1-4H3 InChIKey = HJJSDJHRTMFJLP-UHFFFAOYSA-N Alternate Names: TMS-butynol. Physical Data: bp 83–85 °C (13 mmHg). Solubility: highly soluble in all standard organic solvents (hexanes, toluene, CH2Cl2, EtOAc, alcohols, ethers). Partially soluble in water. Form Supplied in: colorless to light yellow liquid; racemic compound is commercially available. Nonracemic material must be prepared. Handling, Storage, and Precautions: limited data are available for 4-TMS-3-butyn-2-ol. Prudent laboratory practices for handling chemicals should be followed. Use in a fume hood with adequate ventilation. Preparative Methods: racemic 4-trimethylsilyl-3-butyn-2-ol can be prepared by deprotonation with strong bases (BuLi, LDA, Grignard reagents) of trimethylsilylacetylene followed by addition to acetaldehyde.1 Deprotonation of 3-butyn-2-ol followed by quenching with excess trimethylsilyl chloride followed by concomitant hydrolysis of the trimethylsilyl ether is generally the most straightforward route.2 Enzymatic reduction of 4-TMS-3-butyn-2-one has also been used to prepare the reagent using alcohol dehydrogenase.3 Preparation of nonracemic 4-TMS-3-butyn-2-ol has been accomplished by asymmetric addition of dimethylzinc to acetaldehyde promoted by TADDOL4 or addition of a trimethylsilylvinylsulfoxide to acetaldehyde followed by thermal elimination of the sulfoxide.5 Asymmetric reduction of 4-TMS-3-butyn-2-one using stoichiometric reducing reagents,6 catalytic transfer hydrodrogenation,7 and enzymatic reduction with isolated protein or whole cells afford the 4-TMS-3-butyn-2-ol with varying degrees of enantioenrichment.8 Enzymatic resolution by esterification of the racemic alcohol is the method of choice for the large-scale preparation.9