Terminal acetylene derivatives, with

Several acetylene derivatives were prepared by alkylation of the terminal acetylene 56 with the requisite alkyl iodides followed by trityl deprotection (Scheme... 

The terminal acetylene derivatives Osg(CO)i6(RCCH) (R = Me, Et, Ph) have been shown to react with CO to give Osg(CO)i7(RCCH), (89), in which the acetylene ligand is still intact and sits on the base of the capped pyramidal osmium polyhedron. This compound was found to convert by the action of heat to an isomer in which the proton from the acetylene has been transferred to the metal array. The process is accompanied by an opening up of the metal cluster (Scheme 34). 

A variety of alkynyl derivatives, including trimethylsilyl acetylene and terminal acetylene derivatives, have also been prepared by delithi-ation reactions with N3P3F6 (77, 79). The terminal silyl group of the trimethylsilyl acetylene derivatives has been substituted by H using KF and EtOH. The alkynyl groups of some of these substituted phos-phazenes have been found to react with Co2(CO)8, forming Co2(CO)6 complexes (77). 

Palladium-catalyzed addition of trimethylgermyl cyanide to terminal acetylenes proceeded with high 2 selectivity (Scheme 11.31) [50]. Application of this addition to the formation of germole derivatives has been reported (Scheme ll 32) [51]... 

Aminoalcohols can be used for Friedel-Crafts syntheses with remarkable efficiency . Alcohols and acids have been prepared and olefins synthesized from terminal acetylene derivatives via gc/n-diboro compounds . 

Ethylene from acetylene derivatives with protection of terminal carbon-carbon triple bonds as silylacetylenes... 

Methyl ketones are important intermediates for the synthesis of methyl alkyl carbinols, annulation reagents, and cyclic compounds. A common synthetic method for the preparation of methyl ketones is the alkylation of acetone derivatives, but the method suffers limitations such as low yields and lack of regioselectivity. Preparation of methyl ketones from olefins and acetylenes using mercury compounds is a better method. For example, hydration of terminal acetylenes using HgSO gives methyl ketones cleanly. Oxymercuration of 1-olefins and subsequent oxidation with chromic oxide is... 

The polar tellurium(II)-nitrogen bond is readily susceptible to protolysis by weakly acidic reagents. Eor example, the reaction of [Te(NMe2)2]oo with two equivalents of Ph3CSH produces the monomeric thiolato derivative Te(SCPh3)2. Alkynyl tellurides may be prepared by the reaction of terminal acetylenes with arenetellurenamides (Eq. 10.13). ... 

Nonactivated terminal acetylenes have been added to enamines derived from aldehydes. A long reaction time or catalysis by copper(I) chloride is necessary. Thus the enamine (16) formed the adduct (72) on heating with phenylacetylene (64). 

The above-postulated overall mechanism considers two alternative pathways depending on the nature of the acetylene derivative. Region A outlines a proposal in which the formation of the a-complex intermediate is supported by the fact that the treatment of aliphatic terminal acetylenes with FeCl3 led to 2-chloro-l-alkenes or methyl ketones (Scheme 12). The catalytic cycle outlined in region B invoked the formation of the oxetene. Any attempt to control the final balance of the obtained... 

The pincer-type palladacycle (120) (R = 1Pr), which is actually a derivative of a dialkylphos-phinous acid (themselves excellent ligands see Section 9.6.3.4.6) was shown to allow the crosscoupling of aryl chlorides with terminal acetylenes ((120), ZnCl2, Cs2C03, dioxane, 160 °C). However the high reaction temperature may be prohibitive for the actual application of this catalytic system, as acetylenes are known to be thermally sensitive.433 The same palladacycle (R = Ph) is effective in the Suzuki-Miyaura reaction with aryl bromides and activated aryl chlorides (K2C03, toluene, 130 °C). 

Dialkynyl tellurides are obtained in moderate yield by the one-pot reaction of TeCl4 with LiN(SiMe3)2, followed by the addition of a terminal acetylene. Alkenyl tellurium(II) derivatives may also be prepared by the addition of arenetellurenamides or Te[N(SiMe3)2]2 to the C = C bond of dimethylacet-ylene dicarboxylate.180... 

The Fukuyama indole synthesis involving radical cyclization of 2-alkenylisocyanides was extended by the author to allow preparation of2,3-disubstituted derivatives <00S429>. In this process, radical cyclization of 2-isocyanocinnamate (119) yields the 2-stannylindole 120, which upon treatment with iodine is converted into the 2-iodoindole 121. These N-unprotected 2-iodoindoles can then undergo a variety of palladium-catalyzed coupling reactions such as reaction with terminal acetylenes, terminal olefins, carbonylation and Suzuki coupling with phenyl borate to furnish the corresponding 2,3-disubstituted indoles. 

Some acetylenic (with a non-terminal triple bond) or allenic compounds, RCH=C CH2, can be transformed into alkali metal derivatives of terminal acetylenes by treatment with a very strong base. Treatment of an acetylenic compound with the grouping CHjCsC- or CH3C=CCH=CH- with one equivalent of an alkali amide (preferably the soluble potassium... 

The reaction of trimethylsilylated terminal alkynes with iodoarenes can be performed under 1 atm CO pressure in the presence of dppf complex of palladium, and BU4NF at room temperature (Equation (23)). As trimethylsilyl derivatives of terminal acetylenes are known to undergo facile cleavage by fluoride ions, this reaction actually involves not the organosilicon compound, but acetylenide nucleophile. The method has been successfully applied to the modification of uracyl deoxynucleosides. 

The halogenated derivatives of oxazoles, thiazoles80 and benzothiazoles81 were also the subject of palladium catalyzed coupling with terminal acetylenes. 5-Bromo-2-methyl-4-phenyloxazole for example coupled efficiently with phenylacetylene using a conventional catalyst system to give an excellent yield of the desired product (6.53.),82... 

Pattenden and Schulz have reported that treatment of the acetylene derivative 43 with (TMS)3SiH leads, in one pot, to the bicyclic compound 44 in 70% yield (equation 71)". The proposed mechanism involves (TMS)3Si radical addition to the triple bond to form a vinyl radical followed by a remarkable cascade of radical cyclization-fragmentation-transannulation-ring expansion and termination via ejection of the (TMS Si radical to afford the bicyclic product. 

The reaction sequence in steps two and three is known as the Corey-Fuchs method to create an alkyne from an aldehyde 10 Reaction of triphenylphosphane with carbontetrabromide gives phenylphosphane-dibromomethylene. This reagent then transforms aldehyde 19 into the corresponding dibromoalkene 20 thereby extending the chain by one carbon. Reaction of the bromo compound with two equivalents of n-butyllithium in THF at -78 °C results in the rapid formation of the acetylenic lithio derivative which forms the terminal acetylene 21 upon aqueous work-up. 

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