6999-19-5

Basic information

• Product Name: 4-TRIMETHYLSILYL-3-BUTYN-2-OL
• Synonyms: 4-Trimethylsilyl-3-butynol, t;4-(triMethylsilyl)but-3-yn-2-ol;TIMTEC-BB SBB009027;1-TRIMETHYLSILYLBUT-1-YNE-3-OL;(+/-) 4-TRIMETHYLSILYL-3-BUTYN-2-OL;4-TRIMETHYLSILYL-3-BUTYN-2-OL;4-TRIMETHYLSILYL-3-BUTYN-2-OL (+/-);4-(Trimethysilyl)-3-butyn-2-ol
• CAS NO: 6999-19-5
• Molecular Formula: C₇H₁₄OSi
• Molecular Weight: 142.27
• Product Categories: Alkynes;Building Blocks;Chemical Synthesis;Internal;Organic Building Blocks;Acetylenes;Acetylenic Alcohols & Their Derivatives;Ethynylsilanes;Si (Classes of Silicon Compounds);Si-(C)4 Compounds
• Mol File: 6999-19-5.mol
• Article Data: 56

Chemical Properties

• Boiling Point: 76 °C
• Flash Point: 143 °F
• Appearance: /
• Density: 0.847 g/mL at 25 °C
• Vapor Pressure: 0.477mmHg at 25°C
• Refractive Index: n 20/D 1.446
• Storage Temp.: 2-8°C
• Solubility: highly soluble in all standard organic solvents (hexanes, toluene, CH2Cl2, EtOAc, alcohols, ethers). Partially soluble in water.
• PKA: 13.78±0.20(Predicted)
• BRN: 1923632
• CAS DataBase Reference: 4-TRIMETHYLSILYL-3-BUTYN-2-OL(CAS DataBase Reference)
• NIST Chemistry Reference: 4-TRIMETHYLSILYL-3-BUTYN-2-OL(6999-19-5)
• EPA Substance Registry System: 4-TRIMETHYLSILYL-3-BUTYN-2-OL(6999-19-5)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26
• RIDADR: 1993
• WGK Germany: 3
• TSCA: No
• HazardClass: 3
• PackingGroup: III
• Hazardous Substances Data: 6999-19-5(Hazardous Substances Data)

Usage

Chemical Properties

Colorless liquid

Physical properties

bp 83–85°C (13 mmHg).

Uses

More recently, Mulzer has reported use of the corresponding allenylsilane derived from 4-TMS-3-butyn-2-ol for use in the synthesis of the C13–C18 fragment of branimycin (eq 2).

Preparation

racemic 4-trimethylsilyl-3-butyn-2-ol can be prepared by deprotonation with strong bases (BuLi, LDA, Grignards reagents) of trimethylsilylacetylene followed by addition to acetaldehyde.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.Enzymatic reduction of 4-TMS-3-butyn-2-one has also been used to prepare the reagent using alcohol dehydrogenase.Preparation of nonracemic 4-TMS-3-butyn-2-ol has been accomplished by asymmetric addition of dimethylzinc to acetaldehyde promoted by TADDOL or addition of a trimethylsilylvinylsulfoxide to acetaldehyde followed by thermal elimination of the sulfoxide.Asymmetric reduction of 4- TMS-3-butyn-2-one using stoichiometric reducing reagents, catalytic transfer hydrodrogenation,and enzymatic reduction with isolated protein or whole cells afford the 4-TMS-3-butyn- 2-ol with varying degrees of enantioenrichment.Enzymatic resolution by esterification of the racemic alcohol is the method of choice for the large-scale preparation.

InChI:InChI=1/C7H14OSi/c1-7(8)5-6-9(2,3)4/h7-8H,1-4H3

Upstream product

• 75-77-4 chloro-trimethyl-silane 
• 2028-63-9 but-3-yn-2-ol 
• 109-72-8 n-butyllithium 
• 5272-36-6 3-trimethylsilyl-2-propyn-1-ol 
• 75-07-0 acetaldehyde 
• 1066-54-2 trimethylsilylacetylene 
• 74-88-4 methyl iodide 
• 925-90-6 ethylmagnesium bromide 
• 108-05-4 vinyl acetate 
• 103253-60-7 4-trimethylsilyl-3-butyn-2-ol 
• 163931-16-6 (S)-3-(tert-Butyl-dimethyl-silanyloxy)-1-trimethylsilanyl-but-1-yne 
• 344580-04-7 2,2,2-trifluoroethyl 2,2,3,3-tetrahydroperfluoroundecanoate 
• 472954-96-4 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-Heptadecafluoro-undecanoic acid (S)-1-methyl-3-trimethylsilanyl-prop-2-ynyl ester 
• 401614-03-7 1-phenylseleno-1-[(S)-p-tolylsulfinyl]-2-(trimethylsilyl)ethane 

Downstream Products

• 129571-78-4 (R)-4-trimethylsilyl-3-butyn-2-yl acetate 
• 6999-19-5 (S)-4-trimethylsilyl-3-butyn-2-ol 
• 146514-00-3 4-trimethylsilylbut-3-yn-2-yl benzoate 
• 1026984-69-9 C₂₁H₂₃NO₅Si 
• 121522-26-7 5-((tert-butyldimethylsilyl)oxy)pent-3-yn-2-yl diethyl phosphate 
• 462660-39-5 C₂₅H₃₄O₂Si₃ 
• 146566-29-2 (E)-trimethyl-(1-phenyl-but-2-enyl)-silane 
• 148522-69-4 (Z)-4-trimethylsilylbut-3-en-2-yl benzoate 
• 146513-67-9 (Z)-4-trimethylsilylbut-3-en-2-yl N-phenylcarbamate 
• 867375-26-6 [(4-trimethylsilyl-3-butyn-2-oxy)dimesitylsilyl]trimethylstannane 
• 1182221-95-9 methyl (2S,5R,6S)-2-ethyl-5-((4-methoxybenzyloxy)methyl)-2,6-dimethyl-3-oxo-8-(trimethylsilyl)oct-7-ynoate 

Relevant articles and documents

Propargylation of CoQ0 through the Redox Chain Reaction

An efficient catalytic propargylation of CoQ0 is described by employing the cooperative effect of Sc(OTf)3 and Hantzsch ester. It is suggested to work through the redox chain reaction, which involves hydroquinone and dimeric propargylic moiety intermediates. A broad range of propargylic alcohols can be converted into the appropriate derivatives of CoQ0 containing triple bonds in good to excellent yields. The mechanism of the given transformation is also discussed.

Towards the Total Synthesis of Jerangolids – Synthesis of an Advanced Intermediate for the Pharmacophore Substructure

The jerangolids are a class of natural products with a skipped diene substructure isolated from Sorangium cellulosum. Here, we present a new strategy for the total synthesis of these compounds based on a skipped diyne as central building block and a suitably substituted epoxy aldehyde as building block for the dihydropyran substructure. So far, we reached an advanced intermediate which is related to the pharmacophore subunit of the jerangolids as well as of the ambruticins. A key step is a Shi epoxidation with high e.r. to form the epoxy aldehyde. Both building blocks are coupled in a Carreira alkynylation, where additional mechanistic studies based on DFT calculation were realized. The alkynylation is followed by a nucleophilic 6-endo-tet epoxide opening to form the pyran structure and a Nicholas reduction to remove a propargylic OH group.

Phosphine-Catalyzed Intermolecular Annulations of Fluorinated ortho-Aminophenones with Alkynones – The Switchable [4+2] or [4+2]/[3+2] Cycloaddition

A phosphine-catalyzed intermolecular annulation reaction of functionalized ortho-aminoacetophenones with alkynones has been disclosed in this paper. A variety of 2-alkynylquinolines and benzo-fused indolizine were selectively afforded in moderate to good yields at different reaction temperatures and with different phosphine catalysts via the in situ generated zwitterionic intermediate derived from alkynone and phosphine. (Figure presented.).