Silyl anions acetylenes

Monosubstitution of acetylene itself is not easy. Therefore, trimethylsilyl-acetylene (297)[ 202-206] is used as a protected acetylene. The coupling reaction of trimethylsilylacetylene (297) proceeds most efficiently in piperidine as a solvent[207]. After the coupling, the silyl group is removed by treatment with fluoride anion. Hexabromobenzene undergoes complete hexasubstitution with trimethylsilylacetylene to form hexaethynylbenzene (298) after desilylation in total yield of 28% for the six reactions[208,209]. The product was converted into tris(benzocyclobutadieno)benzene (299). Similarly, hexabutadiynylben-zene was prepared[210j. 

Silyl, germanyl and stannyl alk-l-ynyl ketones have been prepared from 2-lithio-2-(trimethylsilylethynyl)-l,3-dioxolane 448. The deprotonation of the dioxane 447 with n-BuLi at — 65 °C afforded the acyl anion 448 which, after reaction with trimethylsilyl, trimethylgermanyl and trimethylstannyl chloride, gave the expected derivatives (Scheme 117)658. Hydrolysis of these products with 0.01 M sulfuric acid at room temperature in aqueous acetone gave the corresponding acyl derivatives 449. On the other hand, the reaction of the intermediate 448 with alkyl halides allows the synthesis of acetylenic ketones659. 

Conjugate addition of the complete allylic alcohol fragment is possible with the mixed cuprate reagents 33 prepared by asymmetric reduction (chapter 26) of acetylenic ketones 29 to give the alcohols 30, protection as a silyl ether 31 and hydroboration-iodination. Lithiation and reaction with hexynyl copper (I) gives the mixed cuprate 33 from which the less stable anion is transferred selectively to an enone.3 This approach has been widely used in the synthesis of prostaglandins. 

In the area of 2, 3 -didehydro-2, 3 -dideoxynucleosides, a new route to compounds of this type in the pyrimidine series is outlined in Scheme 4. The thioglycoside 54 was produced directly from deoxyribose and thiophenol in acidic conditions, and the condensations to form the nucleoside derivatives were P-selective by about 2 l/ A full account has been given of the formation of 2, 3 -didehydro-2, 3 -dideoxy systems from 2, 3 -dimesylates, protected at 0-5, by treatment with telluride anion (see Vol. 27, p. 247)7 Treatment of the furanoid glycal 55, made by cyclization of an acetylenic alcohol (Chapter 13), with silylated thymine in the presence of iodine, followed by sodium methoxide, provides a new route to d4T (56)7 A new synthesis of d4T (56) from 5-methyluridine has also been described, as has a route to d4T labelled with at C-1, which starts from [l- C]-ribose and proceeds via [r- C]-5-methyluridine, convertible in very high yield to [l - C]-d4T. ... 

The necessary silyl triflone reagents proved difficult or irr5>os-sible to make with less hindered silanes (TMS or TBDMS) by the reaction of the silyl-acetylene anion ( -BuLi/Et20/—78 °C) with Tf20. It was this triflation which failed with the proximal ethers and substituted acetylenes above. 

Propargylic Anion Equivalent. (TMS)allene reacts with electrophiles at the C-3 position in an Se2 process analogous to electrophilic substitution reactions of allyl- andpropargylsilanes. For example, upon treatment with trimethylsilyl chlorosulfonate or sulfur trioxide-1,4-dioxane, (TMS)allene yields silyl esters of sulfonic acids (eq 3). (TMS)allene undergoes conjugate addition with a, 8-unsaturated acyl cyanides to yield 5,e-acetylenic acyl cyanides. ... 

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