Homogeneous catalysis alkynes

Khan, M. M. T. 1974, Homogeneous Catalysis by Metal Complexes, Vol. II, Activation of Alkenes and Alkynes, Academic Press New York - London... 

As with carboxylic acids obtained by palladium hydroxycarbonylation, their derivatives esters, amides, anhydrides and acyl halides are synthesized from alkenes, CO and HX (X = OR, NR2 etc.). The Pd-catalyzed methoxycarbonylation is one of the most studied reactions among this type of catalyzed carbonylations and has been reviewed and included in reports of homogeneous catalysis.625, 26 The methoxycarbonylation has been applied to many different substrates to obtain intermediates in organic syntheses as well as specific products. For instance, the reaction has been applied for methoxycarbonylation of alkynes666 Highly efficient homogeneous Pd cationic catalysts have been reported and the methoxycarbonylation of alkynes has been used to develop economically attractive and environmentally benign process for the production of methyl... 

The author hopes that this chapter has convinced the readers of the value of homogeneous catalysis for the synthesis of organophosphorus compounds and for organo-heteroatom compounds in a broader sense. Hydrosilylation and hydroboration are indispensable modern synthetic reactions in this category. The H-P addition reactions herein described joins them as a third member. Although this chapter does not cover, the addition reactions of the S-P and Se-P bonds in thiophosphates [39] and selenophosphates [40] to alkynes also proceed in the presence of transition metal catalysts. In view of the wide use of phosphorus compounds, the new procedures will find practical applications. 

M. M. T. Khan and A. E. Martel, Homogenous Catalysis by Metal Complex Activation of Alkenes and Alkynes" Academic Press, New York, 1974. 

Heterometal alkoxide precursors, for ceramics, 12, 60-61 Heterometal chalcogenides, synthesis, 12, 62 Heterometal cubanes, as metal-organic precursor, 12, 39 Heterometallic alkenes, with platinum, 8, 639 Heterometallic alkynes, with platinum, models, 8, 650 Heterometallic clusters as heterogeneous catalyst precursors, 12, 767 in homogeneous catalysis, 12, 761 with Ni—M and Ni-C cr-bonded complexes, 8, 115 Heterometallic complexes with arene chromium carbonyls, 5, 259 bridged chromium isonitriles, 5, 274 with cyclopentadienyl hydride niobium moieties, 5, 72 with ruthenium—osmium, overview, 6, 1045—1116 with tungsten carbonyls, 5, 702 Heterometallic dimers, palladium complexes, 8, 210 Heterometallic iron-containing compounds cluster compounds, 6, 331 dinuclear compounds, 6, 319 overview, 6, 319-352... 

The status for homogeneous catalysis by gold in solution was dramatically transformed in 1998 by the results of Teles et al.11 This BASF group described the use of cationic Au1 complexes of the type [L-Au+] (where L is a phosphane, phosphite or arsine) for the addition of alcohols to alkynes in the presence of a Lewis or Brpnsted acid as a co-catalyst in methanol at 313 K. An example of such a reaction is the conversion of 3-hexyne to 3,3-dimethoxyhexane ... 

Gold(l) complexes of alkenes and alkynes appear to play an important role as intermediates of the gold(l)-catalyzed addition of water, alcohols, carboxylic acids, or amines to these substrates. The elfect of this 7r-complexation (22) is superior to the performance of mercury(ll) in this type of reactions. " In a similar way, gold(III) salts have found applications in homogeneous catalysis. ... 

MF5 and MCI5 are strongly electrophilic see Electrophile and Electrophilic Reaction) and catalyze Friedel-Crafts reactions. The HF/TaFs system is a superacid catalyst and has been used in the selective acid-catalyzed isomerization and hydrogenolysis of cycloalkanes. Oligomerization and polymerization of alkynes with Nb and Ta halides as catalysts have been reported see Oligomerization Polymerization by Homogeneous Catalysis) ... 

Not unexpectedly, more reactive ligands like alkynes undergo acid-promoted transformations such as the cyclodimerization in equation (4) see Oligomerization Polymerization by Homogeneous Catalysis). 

Metal complex chemistry, homogeneous catalysis and phosphane chemistry have always been strongly connected, since phosphanes constitute one of the most important families of ligands. The catalytic addition of P(III)-H or P(IV)-H to unsaturated compounds (alkene, alkyne) offers an access to new phosphines with a good control of the regio- and stereoselectivity [98]. Hydrophosphination of terminal nonfunctional alkynes has already been reported with lanthanides [99, 100], or palladium and nickel catalysts [101]. Ruthenium catalysts have made possible the hydrophosphination of functional alkynes, thereby opening the way to the direct synthesis of bidentate ligands (Scheme 8.35) [102]. 

In the field of homogeneous catalysis the metathesis of unsaturated hydrocarbons offers many intriguing possibilities for producing important intermediates and end products from alkenes and alkynes. Through major advances in catalyst design in recent years, metathesis has become an important synthetic route to be considered in chemical laboratories whenever a special organic product has to be obtained. In fine chemistry metathesis is a very valuable reaction for the synthesis of natural compounds. Metathetical polymerization has been accepted by the industry as a viable means for producing polymers. 

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