L-Trimethylsilyl-3- propyne

Rhodium-catalyzed silylformylation proceeds smoothly in branched 1-alkynes at 25 °C as shown in Table 3. The stereochemistry at the chiral carbon involved in alkynes is retained intact under the silylformylation conditions. (A)-28, (rhodium particles co-condensed with mesitylene. 3-Trimethylsilyl-l-propyne 40 reacts similarly to give 41 (Equation (7)). " / //-Butylacetylene does not work as a substrate for the silylformylation because of the bulky tert-huty group on the i/>-carbon. In contrast to /< r/-butylacetylene, trimethylsilylacetylene 42 gives 43 in a fair yield (Equation (8)). ... 

Butyllithium, 56 Organozinc reagents, 220 3-Trimethylsilyl-l-propyne, 329 Cross-coupling of alkyl + vinyl groups Iodosylbenzene, 151 Methyl N-benzyloxycarbonyl-a-chloro-glycinate, 186... 

Trimethylsilyloxyethylene, 274, 299 3-Trimethylsilyl-l-propyne, 329 Trimethylsilyl trifluoromethanesul-fonate, 118, 149, 187, 321, 329 Trimethyl(trichloromethyl)silane, 336 Triphenylsilane, 334 Triphenylsilane-Di-t-butyl peroxide, 334... 

The a-silylmethyl esters (252), potentially useful as precursors to ot-methylene esters can be prepared by additions of l-ethoxy-3-trimethylsilyl-l-propyne to a wide variety of both saturated and... 

Alkylation and hydroxyalkylation of allenic sulfides, 46 -(22) 4-Phenyl-l-butyne, 48 - (23) l-Chloro-5-hexyne, 48 - 24) 3-Buty-noic acid, 49 - (2S) 2,3-Pentadienedioic acid, 50 - (2S) 2-riethyl-2,3--pentadienedioic acid, 51 - (37) 3-Trimethylsilyl-l-heptyne, 52 - 23) 3-Ethynyl-l-hexanol, 53 - (29) 3-Phenyl-3-trimethylsilyl-l-propyne,... 

Propargylation Reactions. 3-Trimethylsilyl-l-propyne is metalated easily by using an organomagnesium or a lithium compound, leading to the corresponding alkynic organometallic reagent which can react with many electrophiles. 

Alkylations. 3-Trimethylsilyl-l-propyne gets deprotonated twice using a strong base, after which it can be added to an electrophile (eq 29). ... 

Metal Alkynilide Additions to Aldehydes, Ketones, Imines, and Nitrones. 3-Trimethylsilyl-l-propyne is transformed into the con esponding metal alkynilide by treatment with a catalytic amount of an amine base and a metal tiiflate. These metal alkynilides give an addition reaction, for example, to nitrones (eq 30). ... 

Hydrozirconation and Zirconium-catalyzed Carboalumina-tion. Hydrozirconation of 3-trimethylsilyl-l-propyne using Schwartz s reagent gives the alfcenylzirconocene that can be further reacted to provide 1,3-dienes after Lewis-acid-catalyzed addition to aldehydes (eq 35), vinyl sulfones from reaction with sulfonyl chlorides (eq 36), and allylsilanes upon transmetalla-tion with CuBr followed by 1,4-addition (eq 37)." ... 

The nickel-catalyzed synthesis of 1,3-dienes has been reported utilizing the reactivity of 3-trimethylsilyl-l-propyne (eq 46). ... 

Trimethylsilyl-l-propyne reacts as the dipolarophile with an in situ generated cyclic carbonyl ylide to give two cycloadduct products in an 86 14 ratio (eq 53). ... 

---