Ruthenium catalysis addition

Dienes such as 90 can be accessed by a multi-component reaction under ruthenium catalysis involving an allene 88 and an enone (methyl vinyl ketone in this case), with cerium(m) chloride as an additive in DMF (Scheme 26).95,96 With an allene concentration of 0.25 M, yields are moderate to good. Different ruthenium catalysts and additives were tested in order to optimize this reaction. CpRu(COD)Cl 89 and CpRu(MeCN)3PF6 appeared to be more versatile ones. The mono-, di-, tri-, and tetrasubstituted allenes have been investigated with methyl vinyl... 

Diisopropenyl oxalate results from the addition of oxalic acid to propyne. The ester condenses with all types of amines under ruthenium catalysis to yield the corresponding ester amides or oxamides, depending on the amounts of amines used (equation 104)327. 

The addition of carbonyl-functionalized arenes to electron-rich alkenes and alkenes is achieved under ruthenium catalysis (Murai reaction) S. Murai, F. Kakiuchi, S. Sekine, Y. Tanaka, A. Kamatani, M. Sonoda, N. Chatani, Nature 1993, 366, 529-531. 

The previous examples have established ruthenium-catalyzed atom-transfer reactions as a valuable addition to the list of synthetic methods available in fine chemistry. The potential of these systems is obvious, but sometimes their applicability is limited by rather poor catalytic activity and/or selectivity, particularly when it comes to the chemoselectivity of the addition and the concurrent formation of telomers. Hence, the need to extend the range of possible substrates and to perform the reactions under milder conditions led to the search for new catalytic systems with improved performances. Yet, the application of ruthenium catalysis to radical reactions remains a relatively unexplored and new field. 

In addition to these intramolecular [2+2+2] cycloadditions, intramolecular [4+2] cycloaddition of yne-enones 29 leading to fused pyrans 30 has been achieved by means of the ruthenium catalysis with a cationic complex, CpRu(MeCN)3PF6 (Eq. 15) [24], Such hetero Diels-Alder cycloaddition was considered to proceed via an oxaruthenacycle 31. 

The elTiciency of cobalt and ruthenium catalysis is not very sensitive to the presence of promoters )21]. With cobalt, the addition of thorium and alkali promoters increases wax production and supports were incorporated to increase the active metal surface area. On the other hand, promoters and supports are essentia) for iron catalysts. 

It is now usual to promote these cycloadditions by catalysts for example, reaction with A -tosyl-ynamides, using ruthenium or copper catalysts, giving 1-substituted 5- and 4-amino triazoles, respectively the formation of the 1,4-substitution pattern with copper catalysis and 1,5-pattem with ruthenium catalysis seems to be general. The latter metal will also promote addition to internal alkynes. ... 

As carboxylic acid additives increased the efficiency of palladium catalysts in direct arylations through a cooperative deprotonation/metallation mechanism (see Chapter 11) [45], their application to ruthenium catalysis was tested. Thus, it was found that a ruthenium complex modified with carboxylic acid MesC02H (96) displayed a broad scope and allowed for the efficient directed arylation of triazoles, pyridines, pyrazoles or oxazolines [44, 46). With respect to the electrophile, aryl bromides, chlorides and tosylates, including ortho-substituted derivatives, were found to be viable substrates. It should be noted here that these direct arylations could be performed at a lower reaction temperatures of 80 °C (Scheme 9.34). 

A nice addition to this work was made by Ellman and coworkers [100], who reported an intramolecular cyclization of aromatic ketones using Cp Rh (C2H3SiMe3)2 as catalyst (Scheme 19.69). This rhodium-catalyzed reaction was more efficient with respect to ruthenium catalysis (about 20% yield with RUH2 (CO)(PPh3)3), but its scope was limited to substrates bearing noniso-merizable olefins. 

Two mechanistic pathways, which differed in the way of ruthenium-mediated initial cleavage of formyl C-H or amido N-H bond, were proposed for the catalytic cycle. As shown in Scheme 7.3, an irreversibly cleavage of formyl C-H bond by the active ruthenium complex was followed by reversible insertion of the olefin into the Ru-H bond, which afforded either six-membered or seven-membered ruthenacycle. After reductive elimination, indolin-2-ones or 3,4-dihydroquinolin-2-one was formed. According to isotopic studies, pathway leading to six-membered lactams is postulated to be less favored. Another cyclization process initiated by Ru-catalyzed oxidative addition of formyl N-H bond (Scheme 7.4) was similar to Carreira s proposal for their hydrocarbamoyla-tion reaction of allylic formamides under similar ruthenium catalysis conditions [7]. The 6-endo cyclization process is proposed to be favored under the catalytic system B. 

Kundig and co-workers demonstrated in 2010 a proof of concept of chiral ruthenium catalysis for arylthiol addition to enones. ° The well-defined and stable ruthenium complexes based on (/ ,/ )-BIPHOP-F ligand 258 was tested, but the best results were obtained when cyclohexenone and... 

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