Hydrodimerization, of activated

Intramolecular hydrodimerization of activated olefins has been exploited for elegant one-step cyclizations and heterocouplings (Fig. 53) [263, 278, 279]. 

The formation of dimers by reduction of a,p-unsaturated ketones in aqueous media is well documented in the early literature of electrochemistry. Reductants include sodium or aluminium amalgams [58], dissolving zinc and a lead cathode in both acid and alkaline conditions [59,60]. Mixtures of dimers and dihydro derivatives were isolated. As the concept of the hydrodimerization of activated alkenes... 

Cathodic hydrodimerization of active olefins and carbonyl compounds. 

In addition to the cathodic hydrodimerization of activated olefins [see 3.2.1.1], the electrosyntheses of substituted benzaldehydes are among the few electroorganic reactions which are carried out on a large scale industrially. 

In addition to the cathodic hydrodimerization of activated olefins and the Kolbe reaction, the anodic dimerization of CH-acidic compounds is another possibility for the electrochemical C—C coupling. Monsanto 281 > has used the anodic dimerization of malonates in a laboratory synthesis of intermediates for useful sequestrants and detergency builders. 

Anodic dimerization of electron-rich olefins, the mirror image process to cathodic hydrodimerization of activated olefins (Sect. 12.2), affords a one-step synthesis for substituted butanes(Eq. (175) ) 268)( dienes (Eq. (176) ) 26S precursors of polyenes (Eq. (177)) 36,385 and 1,4-dicarbonyl compounds (Eq. (178)) 35>36). 

Electrolytic formation of carbon-carbon bonds occurs in the reduction of ketones to pinacols, in the Kolbe synthesis, and in the hydrodimerization of activated double bonds. Of these only the last reaction has been used in the preparation of heterocyclic compounds. 

Hydrodimerization of activated alkenes is a well-established process. 7r-Electron-deficient heteroaromatic compounds activate a double bond similarly to a cyano or car-bethoxy group, and in accordance with that analogy vinylpyridines can be hydrodimer-ized. 4-Vinylpyridine [380] forms l,4-bis-(4-pyridyl)butane in 82% yield on electrolysis in a mildly alkaline solution containing methyltriethylammonium / -toluenesulfonate and some DMF. The mechanism is discussed in Chapter 21. 

The reductive hydrodimerization of activated olefins was considered as a good test system for initial SECM studies, due to the fact that the dimerization rate constant could be tuned via the substituent activating the olefinic double bond." " For the relatively slow dimerization of the dimethyl fumarate (DF) radical anion, a large UME (25 jam diameter Pt electrode) was employed so that the value of K2 (Equation 7.19) was in the range where the SECM response would be sensitive to the kinetics. Experiments were carried out with solutions of 5.15 and 11.5mM DF in dimethylformamide (DMF), containing 0.1 M tetrabutylammoniumtetrafluoroborate as a supporting electrolyte. The oxidation of -tetramethyl-l,4-phenylenediamine (TMPD), included in solutions at a con-... 

Scheme 5.2-5 Formation of the active Pd-catalyst from [BMIM]2 PCICI4 for the hydrodimerization of 1,3-butadiene.

A wide variety of activated olefins (126) undergo reductive electrochemical dimerization to compounds of structure 127 (electrolytic hydrodimerization) 129 i. While the product 127 is capable of existing in either dl or meso modifications, relatively little attention has been paid to the stereochemistry of hydrodimers... 

Interestingly, various phosphonium salts have been applied [13] as constituents of palladium catalysts for hydrodimerization of butadiene and isoprene about the same time when the results of Kuraray were disclosed. These were obtained by quatemization of aminoalkylphosphines with methyl iodide or HQ (Ph2P-R-NH2 type compounds are known to yield phosphonium salts with these reagents). Although the catalysts prepared in situ from [PdCU] were reasonably active (TOF-s of 10-20 h ) the reactions always yielded complex product mixtures with insufficient selectivity towards the desired 1,7-octadienyl derivatives. 

In order to improve the activity in the absence of co-solvent, the use of a surfactant was studied in the presence of TPPTS-based catalyst [55]. Monflier et al. reported the hydrodimerization of 1 in the presence of surfactants in order to improve butadiene mass transfer in pure water solution [56-58]. Such an additive used in very low amount avoided the presence of an organic co-solvent. It was shown in the case of hydrodimerization that neutral or cationic surfactants played a significant role in the process. Similar behaviors were reported for the telomerization of 1 with 21. While 30% conversion of 1 was achieved in pure water after 24 h reaction time at 50°C using 0.4 mol% of catalyst, the conversion reached 87% when polyether surfactant (POEA) was added to the reaction medium under similar reaction conditions (Table 12). It was found that the conversion is strongly affected by the nature of the surfactant (Table 13). 

Activated methylene components like malonic esters and P-ketoesters can be coupled anodically using small amounts of potassium iodide as redox catalyst (Table 4, No. 4-7) i45-i5n -pj g cathodically formed metallic potassium is used to deprotonate the methylene component generating the oxidizable carbanion. The combination of this reaction with the cathodic hydrodimerization of acrylic esters has been studied several times (Table 4, No. 7) Thus both electrode reac-... 

This section concerns the classical hydrodimerization of alkenes activated by electron-withdrawing substituents, as in Eq. (1). The literature in this area is extensive and this chapter cannot be exhaustive. The focus will be on typical reactions and general conclusions, which may serve as guidelines for further work. Special emphasis will be put on the effect of reaction conditions on the mechanisms, product selectivity, and stereochemistry. Section II.A deals with the monoactivated alkenes, that is, structures of the type 1 where R and R" are H, alkyl, or aryl Sec. II.B deals with intramolecular coupling reactions where two identically activated alkenes are linked together within the same molecule. The reactions of alkenes activated by two electron-withdrawing groups either in a, a- or in a,yS-positions, are treated in Sec. II.C. 

Baizer and coworkers established the most brilliant industrial electroorganic synthesis of the hydrodimerization of acrylonitrile to adiponitrile. They extended this hydrodimerization to a variety of activated olefins and in some cases [41 3] paid attention to the stereochemistry of products. However, their stereochemical data were not enough to discuss the stereochemical course of the reaction. Afterward, an attempt was made to provide a working hypothesis in the hydrodimerization of cinnamates by considering an orientated adsorption of radical anion intermediates on a cathode surface, but this was not persuasive because of a lack of experimental data on the stereochemistry of both the starting olefins and products. Recently Utley and coworkers [44-46] have reported stereochemical data of hydrodimers derived from a variety of cinnamic acid esters with chiral alcohol components. 

The hydrodimerization of non-activated olefins at a platinum electrode affords the corresponding d, /-isomeric products in excess ( > 80%) [57]. 

Seebach and Oei [446,447] reported the asymmetric hydrodimerization of acetophenone (a maximum asymmetric yield of 6.4%) in a chiral cosolvent. The use of small amounts of chiral crown ethers was attempted however, no significant asymmetric induction was observed [443]. It is interesting that in the presence of /5-cyclodextrin, head-to-tail coupling of acetophenone leads to optically active dimeric monoalcohol (ca. 24% ee), whereas the head to head coupling gives optically inactive pinacols [448,449]. 

After the development of the electrolytic reductive coupling of acrylonitrile to adiponitrile (Chapter 21), many investigations have been directed toward developing an alternative, indirect electrolytic process. The electrolytic hydrodimerization reaction in neutral solution [32,33] is critically dependent on the proton activity at the electrode. If the proton activity is too high, the product is predominantly propionitrile, whereas oligo-or polymerization occurs at too low a proton activity. The establishment of a reaction layer with a suitable proton activity in which conditions are favorable for a hydrodimerization of acrylonitrile to adiponitrile is, thus, of paramount importance. This can be accomplished in different ways. 

The key reaction of this 1-octanol process is telomerization of butadiene with a palladium complex catalyst. Known attempts to commercialize the palladium complex-catalyzed telomerization have failed, in spite of great efforts, for the following reasons (1) palladium complex catalysts are thermally unstable and tbe catalytic activity markedly decreases when, as a means of increasing the thermal stability, the ligand concentration is increased (2) a sufficiently high reaction rate to satisfy industrial needs cannot be obtained (3) low selectivity and (4) distillative separation of reaction products and unreacted butadiene from the reaction mixture causes polymeric products to form and the palladium complex to metallize. Kuraray succeeded in 1991 in commercializing the production of 1-octanol using hydrodimerization of butadiene. 

For the hydrodimerization of butadiene with water, attempts have been made to increase the reactivity by adding acidic solids [4], salts such as sodium phosphate [5], emulsifiers [6], carbon dioxide [7], or the like, with no satisfactory results. In particular, the reaction rate increases under a carbon dioxide pressure, but carbonate ions, not carbon dioxide itself, are considered to play an important role in this effect. It is known that the carbonate ion concentration in water is very low even under a carbon dioxide pressure. If the carbonate ion is the true reactant, the reaction rate should increase with the carbonate ion concentration. Since inorganic carbonates show almost no effect, the addition of various tertiary amines having no active hydrogen, under a carbon dioxide pressure was tested [8]. Diamines and bifunctional amines inhibited the reaction. The reaction rate increased only in the presence of a monoamine having a p/f of at least 7, almost linearly with its concentration (Figure 3). 

The large number of synthetically useful intermolecular hydrodimerizations and intramolecular cyclizations of activated olefins to complex carbon skeletons involves in most cases radical anions as key intermediates [152]. 

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