Alkynes to alkenes

In the following section we 11 see another method for converting alkynes to alkenes The reaction conditions are very different from those of Lindlar hydrogenation So IS the stereochemistry... 

A useful alternative to catalytic partial hydrogenation for converting alkynes to alkenes IS reduction by a Group I metal (lithium sodium or potassium) m liquid ammonia The unique feature of metal-ammonia reduction is that it converts alkynes to trans alkenes whereas catalytic hydrogenation yields cis alkenes Thus from the same alkyne one can prepare either a cis or a trans alkene by choosing the appropriate reaction conditions... 

Table 9 3 summarizes reactions that reduce alkynes to alkenes and alkanes... 

Hydrogenation of alkynes to alkenes using the Lindlai catalyst is attractive because it sidesteps the regioselectivity and stereoselectivity issues that accompany the dehydration of alcohols and dehydrohalogenation of alkyl halides. In tenns of regioselectivity, the position of the double bond is never in doubt—it appears in the carbon chain at exactly the sane place where the triple bond was. In tenns of stereoselectivity, only the cis alkene forms. Recall that dehydration and dehydrohalogenation normally give a cis-trans mixture in which the cis isomer is the minor product. 

Hydrogenation of alkynes to alkenes (Section 9.9) Hydrogenation of alkynes may be halted at the alkene stage by using special catalysts. Lindlar palladium is the metal catalyst employed most often. Hydrogenation occurs with syn stereochemistry and yields a cis alkene. 

Addition of Alkenes and/or Alkynes to Alkenes and/or Alkynes Hydro-alkenyl-addition... 

The first experiments on chemoautotrophic theory were carried out by Stetter at the University of Regensburg. It was found that synergy in the FeS/H2S system determined the reductive effect, for example, in the conversion of nitrate to ammonia or of alkynes to alkenes. The conditions used corresponded to those present in hydrothermal systems aqueous phase, 373 K, almost neutral pH and anaerobic conditions (Blochl et al 1992). Two years later, the formation of an amide bond without the use of a condensation agent was successfully demonstrated in the same laboratory (Keller et al 1994). 

Scheme 3.5 Hydrogenation of alkynes to alkenes catalyzed by [RuH 2-H2)(P(CH2CH2PPh2)3)]BPh4 ([Ru] =...

The stereoselective hydrogenation of alkynes to alkenes can be effected by a wide variety of homogeneous catalysts. The appropriate choice of catalyst and reaction conditions allows the selective formation of either the (Z)- or the (l )-a1-kene. Most of the catalysts display a very high chemoselectivity, as they are not reactive towards reducible functional groups such as carbonyl, ester, and double bonds. Many of the details related to catalyst behavior and intricate mechanistic details concerning semihydrogenation of alkynes have often not been unraveled, and will remain a topic of research for the coming years. 

A few remarkable, but rather uncommon, transfer hydrogenations also deserve mention within the context of this chapter namely, the reduction of alkynes to alkenes using a chromium catalyst, and the reduction of double bonds using diimines. 

Quaternary ammonium salts aid the transfer of the hypophosphite anion in the palladium-catalysed reduction of, for example, alkynes to alkenes, nitroarenes to aminoarenes, and in the hydrogenolysis of tetrazolyl aryl ethers to phenols [12-14], It has been demonstrated that the hydrogenolysis is ineffective when preformed tetra-n-butylammonium hypophosphite is employed in a dry homogenous organic solvent [13, 14], For optimum hydrogen transfer, the concentration of hypophosphite relative to the substrate must be controlled at a low level and this is most effectively accomplished with a two-phase system. 

Alkynes may also be hydrogenated, initially to alkenes, and then further to alkanes. By suitable modification of the catalyst, it has proved possible to stop the reaction at the intermediate alkene. Typically, platinum or palladium catalysts partially deactivated (poisoned) with lead salts are fonnd to be suitable for reduction of alkynes to alkenes. Again, syn addition is observed. 

Reduction of alkynes to alkenes. The zinc-copper couple of Smith and Simmons (1, 1292) reduces internal alkynes to (Z>alkcncs exclusively in yields generally >95%.2 Terminal alkynes are reduced to 1-alkenes.3 Example ... 

By comparison with these less interesting reactions, photocyc-loadditions of alkynes to alkenes and related compounds provide a fascinating extension of the analogous reactions for alkenes. The simplest type of cycloaddition yields a cyclobutene (2.99), but depending on the relative absorption characteristics of the substrates and product at the wavelength of irradiation, the cyclobutene may... 

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