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Aluminum alkynes

Aluminum-alkyne interactions were invoked when hydrosilylation of alkynes proceeded in the presence of catalytic amounts of AICI3 or EtAlCl2 [31]. Although most hydrometalations of alkynes occur in a cis configuration, trans-selective hydrosilylation was consistently observed (Scheme 6.14). [Pg.205]

The regioselectivity of the addition of terminal alkynes to epoxides is improved, when the reagents prepared from the lithiated alkynes and either trifluoroborane or chlorodiethyl-aluminum arc employed (M. Yamaguchi, 1983 S. Danishefsky, 1976). (Ethoxyethynyl)lithium-trifluoroborane (1 1) is a convenient reagent for converting epoxides to y-lactones (M. Naka-tsuka, 1990 see p. 327f. cf. S. Danishefsky, 1976). [Pg.64]

In 1968, Eisch and Foxton showed that nickel(II) salts enhance the rate of BU2AIH addition to internal alkynes by a factor of ca. 1000 compared to the process in the absence of a catalyst [26]. Similar catalytic activity of nickel compounds was found for the addihon of aluminum hydrides to alkenes. [Pg.51]

In general, transition metal-catalyzed hydroaluminations of alkynes occur in a syn fashion, i.e., both aluminum and hydride are added to the same face of the 7i-bond. Isomerization of the initially formed vinylalane is usually not observed under the mild reaction conditions used for these transformations. [Pg.66]

As in the P(III) chemistry above, both late metal (Pd) and lanthanide catalysts have been used for P(V)-H additions to alkynes, alkenes, aldehydes, and imines. In addition, titanium, aluminum, and zinc catalysts have been employed. Typical P(V) substrates include dialkyl phosphites P(0R)2(0)H and phosphine oxides PR2(0)H. [Pg.153]

The use of group 4 metallocene alkyne complexes924 and bimetallic aluminum derivatives925 as CL polymerization initiators has also been described. These catalysts generally exhibit poor control with Mn values much lower than expected and Mw/Mn= 1.4-2.6. End groups have not... [Pg.51]

The use of stronger acid conditions provides somewhat better synthetic yields of alkanes from alkynes. A useful method consists of treatment of the substrate with a combination of triethylsilane, aluminum chloride, and excess hydrogen chloride in dichloromethane.146 Thus, treatment of phenylacetylene with 5 equivalents of triethylsilane and 0.2 equivalents of aluminum chloride in this way at room temperature yields 50% of ethylbenzene after 1.5 hours. Diphenylacetylene gives a 50% yield of bibenzyl when treated with 97 equivalents of triethylsilane and 2.7 equivalents of aluminum chloride after 2.8 hours. Even 1-hexyne gives a mixture of 44% n -hexane and 7% methylpentane of undisclosed structure when treated with 10 equivalents of triethylsilane and 0.5 equivalent of aluminum chloride for 0.5 hour.146... [Pg.45]

Flynn et al., also described the synthesis of the fused indoles [73]. The o-iodotrifluoroacetanilide 110 was coupled to aryl alkyne 111 under Sono-gashira conditions followed by subsequent reaction with aryl iodide, 107 with gaseous carbon dioxide produced the fused indole 158. Lewis acid dealkylation with aluminum trichloride produced the deprotected alcohol 159. [Pg.53]

Cationic zirconocene species efficiently activate alkenes toward carbon—carbon bond formation via carbometalation, as has been demonstrated in studies of alkene polymerization. Today, some zirconocene catalysts are available that allow single additions of metal-alkyls (mainly aluminum-alkyls) to alkenes or alkynes, thereby forming stable alkyl- or alkenyl-metals that do not undergo any further oligomerization. On the other hand, carbozirconation with Cp2ZrRCl in the presence of stoichiometric or catalytic amounts of activators has also been realized. [Pg.302]

In 1978, Negishi et al. reported highly regio- and stereoselective methylalumination of alkynes with Me3Al using a zirconocene catalyst [59]. The involvement of cationic zirconocene species in the activation of carbon—carbon triple bonds was suggested in a reaction mechanism featuring electrophilic activation by aluminum (Scheme 8.30). [Pg.303]

Scheme 8.32. Addition of an allyl group from aluminum to an alkyne. Scheme 8.32. Addition of an allyl group from aluminum to an alkyne.
Most of the substrates for these isomerizations have a tetrahedral carbon with at least one hydrogen substituent between the carbonyl group and the alkyne. Due to the comparable high acidity of this C-H bond neighboring the carbonyl group, already a weak base such as a carbonate, a tertiary amine or aluminum oxide can deprotonate this position and a subsequent protonation at the other end of the pro-pargyl/allenyl anion delivers the allene. [Pg.1164]

Equations 1 to 3 show some of fixation reactions of carbon dioxide. Equations la and lb present coupling reactions of CO2 with diene, triene, and alkyne affording lactone and similar molecules [2], in a process catalyzed by low valent transition metal compounds such as nickel(O) and palladium(O) complexes. Another interesting CO2 fixation reaction is copolymerization of CO2 and epoxide yielding polycarbonate (equation 2). This reaction is catalyzed by aluminum porphyrin and zinc diphenoxide [3],... [Pg.80]

The reaction of alkynes with AIX3 at —78 °C has been shown, by NMR spectroscopy, to generate a zwitterionic cr-cyclobutadiene aluminum species 225 (Scheme 58)211a. Transfer of the cyclobutadiene ligand from 225 to a variety of transition metals has been reported211. [Pg.962]


See other pages where Aluminum alkynes is mentioned: [Pg.249]    [Pg.249]    [Pg.227]    [Pg.551]    [Pg.170]    [Pg.35]    [Pg.1028]    [Pg.279]    [Pg.47]    [Pg.50]    [Pg.52]    [Pg.54]    [Pg.67]    [Pg.68]    [Pg.69]    [Pg.353]    [Pg.424]    [Pg.31]    [Pg.283]    [Pg.94]    [Pg.12]    [Pg.80]    [Pg.10]    [Pg.233]    [Pg.234]    [Pg.275]    [Pg.361]    [Pg.365]    [Pg.281]    [Pg.349]    [Pg.44]   
See also in sourсe #XX -- [ Pg.2 , Pg.3 , Pg.11 , Pg.14 ]

See also in sourсe #XX -- [ Pg.2 , Pg.3 , Pg.11 ]




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Alkyne aluminum reagents

Alkynes Aluminum alkyls

Alkynes Aluminum halides

Alkynes lithium aluminum hydride

Alkynes tris aluminum

Aluminum alkyne hydrogenation

Aluminum alkyne interactions

Aluminum reaction with alkynes

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