3-Trimethylsilyl-2-propyn

Trimethylsilyl-2-propyn-l-o1 was obtained from Petrarch Systems, Inc. and used as received. Alternatively, it can be prepared by the silylation of 2-propyn-l-ol ... 

The suspension 1s cooled to 20°C on 1ce and then 800 mL of 1.4 M aqueous sulfuric acid is cautiously added over 0.75 hr so that the temperature remains below 45°C. The resulting solution is stirred for 5 min and then 600 mL of ether is added. Both phases are transferred to a 4-L separatory funnel and the layers are separated. The aqueous phase is extracted twice with 400-mL portions of ether and all ether layers are individually washed in series with two 1-L portions of water and once with 800 mL of saturated sodium chloride solution. The combined organic extracts are dried over magnesium sulfate and concentrated by rotary evaporation. The yellow-brown residue is purified by short path distillation to afford 82-86 g (91-94 yield) of 3-trimethylsilyl-2-propyn-l-ol as a clear, colorless liquid (Note 7), bp 76°C (20 mm) (Note 8). 

Trimethylsilylprop-2-enyl trifluoromethanesulfonate, 2843 3-Trimethylsilyl-2-propyn-1 -ol, 2489b iV-Trimethylsilyl-iV-trimethylsilyloxyacetoacetamide, 3369 Trimethylstibine, see Trimethylantimony, 1316 Trimethylsulfonium chloride, 1299 Trimethylsulfoxonium bromide, 1295 Trimethylthallium, 1317 f 2,4,6-Trimethyltrioxane, 2509 Trinitroacetonitrile, 1005... 

Trimethylsilylmethylmagnesium chloride Magnesium, [chk>ro[(trimethylsilyl)-methyl)- (13170-43-9), 69, 89 3-Trimethylsilyl-2-propyn-1-ol, 66,1, 3 3-Trimethylsilyl-2-propyn-1-yl methanesulfonate, 66, 2... 

Furanes. Hydromagnesiation of 3-trimethylsilyl-2-propyne-l-ol (1) (11, 163) followed by reaction with an aldehyde or ketone provides E-3-lrimethylsilyl-2-alkcne-l,4-diols (2). These are converted into 3-trimethylsilyl-2,5-dihydrofurancs (3) on dehydration... 

Reduction of propargyl alcohols. 3-Trimethylsilyl-2-propyne-l-ol (1), prepared as shown from propargyl alcohol, is reduced stereospecifically by SMEAH to (E)-3-trimethylsilyl-2-propene-1-ol (2). Reductions of propargyl alcohols with LiAIH4 are less rraws-selective. 

B. (EJ-S-Trimethyteilyl-S-ppopen-l-ol, A three-necked, 2-L, round-bottomed flask fitted with a thermometer, nitrogen inlet, 250-mL pressureequalizing addition funnel, and a magnetic stirring bar is charged with 147 mL of a 3.4 M solution of sodium bis(2-methoxyethoxy)aluminum hydride (SMEAH, Note 9) and 200 mL of anhydrous ether (Note 10). The SMEAH solution is cooled to 3°C on ice and then treated dropwise from the addition funnel with a solution of 40 g (0.31 mol) of 3-trimethylsilyl-2-propyn-l-ol in 180 mL of ether over 1.25 hr maintaining the temperature at 5 C or less. Ten minutes after complete addition the ice bath is removed and the reaction is complete... 

The titanium TADDOLATE complex was also used efficiently in the asymmetric addition of dimethyl zinc to 3-trimethylsilyl-2-propynal with and e.e. values over 90% (Schane 21.13). 

The imine 188, derived from 3-(trimethylsilyl)-2-propynal and (S)-a-methyl-benzylamine, was treated at — 40 °C with the born enolate 187 prepared from S-phenyl butanethioate, 9-borabicyclo[3.3.1]nonyl triflate and DIPEA. After workup, a mixture of the anti p-amino acid 189 and the syn adducts 190 was formed in a 5.2 1 ratio. This mixture was then subjected to cyclization using tert-butylmagnesium chloride in diethylether to give the trans P-lactam 191 in... 

Trimethylsilyl-3-rnethylthio-l-propyne, 54 - (32) Trimethyl-silylacetylene, 55 - (32) Bis(trimethylsilyl)acetylene, 56 - (33) 1--Ethoxy-2-trimethylsilylacetylene, 57 - (34) 3-Trimethylsilyl-2 -propyn--l-ol, 58 - (35) 2-Butynoic acid, 59 - (3S) Methyl-1-propynyl sulfoxide,... 

Preparative Methods (i) from 3-trimethylsilyl-2-propyn-l-ol by reduction (sodium bis(2-methoxyethoxy) aluminum hydride (Red-Al), 70%) and acetylation (acetyl chloride, pyridine, 78%) (ii) from 3-trimethylsilyl-2-propyn-l-ol by reduction (P-2 raney nickel, H2, 86%) and acetylation (iii) from ally-loxytrimethylsilane by a metalation-rearrangement sequence (f-butyllithium, 90%) and acetylation (acetic anhydride, triethylamine, 76%). ... 

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