Acetylene coupling

Tellurophene and its mono- and disubstituted derivatives 23 have been prepared in 10-50% yields by coupling acetylene chlorohydrins with NaHTe (Scheme IS) <1987PS119>. 

Acetylene is ideally a very useful reagent for Sonogashira coupling, however, this gas poses selectivity problems in this reaction owing to the propensity for the product to couple with additional halide to form symmetrical constructs. In fact, under the typical conditions, the bis-coupled acetylene 23 has been reported to be the major isolated product from reaction of acetylene (21) and iodobenzene (22 R =... 

As an extension of the 1,3-enyne coupling, acetylene was directly coupled to electrophiles (i.e., carboxaldehydes and imines) in the presence of cationic rhodium catalyst and Brpnsted acid as co-catalyst to provide (Z)-2,4-dienyl allylic alcohols or amines (Scheme 15). a-Ketoesters, activated aldehydes [31, 32], and A-arylsulfonylimine [33] were described as suitable electrophiles for the reductive coupling of acetylene delivering (Z)-dienyl allylic alcohols or amines in a stereocontrolled manner. 

It was discovered in 1940 that some acetylenic chlorides are converted into allenes by treatment with a zinc-copper couple in ethanol. This method appears to... 

To a suspension of a tinc-copper couple in 150 ml of 100 ethanol, prepared from 80 g of zinc powder (see Chapter II, Exp. 18), was added at room temperature 0.10 mol of the acetylenic chloride (see Chapter VIII-2, Exp. 7). After a few minutes an exothermic reaction started and the temperature rose to 45-50°C (note 1). When this reaction had subsided, the mixture was cooled to 35-40°C and 0,40 mol of the chloride was added over a period of 15 min, while maintaining the temperature around 40°C (occasional cooling). After the addition stirring was continued for 30 min at 55°C, then the mixture was cooled to room temperature and the upper layer was decanted off. The black slurry of zinc was rinsed five times with 50-ml portions of diethyl ether. The alcoholic solution and the extracts were combined and washed three times with 100-ml portions of 2 N HCl, saturated with ammonium chloride. 

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. 

The terminal diyne 320 is prepared by coupling of the zinc acetylide 318 with /rfln.s-l-iodo-2-chloroethylenc (319), followed by elimination of HCI with sodium amide[231]. Similarly, terminal di- and triynes are prepared by using cw-l,2-dichloroethylene[232]. The 1-alkenyl or l-aryl-2-(perefluoroalkyl) acetylene 321 is prepared by the reaction of a zinc acetylide with halides[233]. 

Alkynes with EWGs are poor substrates for the coupling with halides. Therefore, instead of the inactive propynoate, triethyl orthopropynoate (350) is used for the coupling with aryl halides to prepare the arylpropynoate 351. The coupling product 353 of 3,3-dicthoxy-l-propyne (352) with an aryl halide is the precursor of an alkynal[260]. The coupling of ethoxy) tributylstan-nyl)acetylene (354) with aryl halides is a good synthetic method for the aryl-acetate 355[261]. 

Palladium also catalyses coupling of haloindolcs with acetylenes. The reaction is carried out in the presence of Cu(I) and presumably involves a copper acetylide as an intermediate[14]. 

Transition-Metal Catalyzed Cyclizations. o-Halogenated anilines and anilides can serve as indole precursors in a group of reactions which are typically cataly2ed by transition metals. Several catalysts have been developed which convert o-haloanilines or anilides to indoles by reaction with acetylenes. An early procedure involved coupling to a copper acetyUde with o-iodoaniline. A more versatile procedure involves palladium catalysis of the reaction of an o-bromo- or o-trifluoromethylsulfonyloxyanihde with a triaLkylstaimylalkyne. The reaction is conducted in two stages, first with a Pd(0) and then a Pd(II) catalyst (29). 

Quantitative aluminum deterrninations in aluminum and aluminum base alloys is rarely done. The aluminum content is generally inferred as the balance after determining alloying additions and tramp elements. When aluminum is present as an alloying component in alternative alloy systems it is commonly deterrnined by some form of spectroscopy (qv) spark source emission, x-ray fluorescence, plasma emission (both inductively coupled and d-c plasmas), or atomic absorption using a nitrous oxide acetylene flame. 

GLASER - CHODKIEWCZ Acetylene Coupling Polyacetylenes from monoacetylenes in the presence of copper salts. 

The stereoselective synthesis of y-bisabolenes was made possible by the development of a new method for the carbosilylation and double alkylation of an acetylenic function coupled with ring closure, overall addition of three carbon substituents to two acetylenic carbons. 

The copper species formed depends on the solvent, and three different species were detected by F NMR, although the structure of each species was not elucidated [245 This copper reagent undergoes a variety of coupling reactions with aryl, alkenyl, allyl, and acetylenic halides [244, 245 (equation 162)... 

Copper(I) halide-catalyzed coupling reactions of perfluoro Gngnard reagents with allyl and propargyl halides have been reported [256], The acetylenic copper compound may be an intermediate in these reactions. 

The arylcopper reagents couple with 1-iodoarylacetylenes to give the unsym-metrical diarylacetylenes [25(S] (equation 176) Reaction with tetrabromoethyl- ene gives bis(pentafluorophenyl)acetylene in 66% yield [25S] (equation 177) Pen-tafluorophenyl copper couples with (bromoethynyl)triethylsilane to give C6F5C=CSi(C2H5)3 in 85% yield [259]... 

C. Cross-Coupling of Halogenopyrazoles with Terminal Acetylenes and Their Copper(I) Salts (Tables X to XV)... 

To ascertain the possibility of inserting more than one acetylenic moiety into the pyrazole ring, the replacement of two and three iodine atoms in the appropriate halides by different alk-l-ynes was carried out. To increase the total rate, the cross-coupling of diiodopyrazoles and triiodopyrazole was performed with higher initial concentrations of the reactants than for the monoiodides. The reaction of diiodopyrazoles with the acetal was completed for the most part in 40 h, and in 64 h in the case of triiodopyrazole. The yields of the di- and triacetals reached 70-90% (Table XTTT). 

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