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Diene ruthenium complexes

Described here is the preparation of (l,5-cyclooctadiene)tricarbonylrutheni-um and its use in the synthesis of tricarbonyl(/7-diene)ruthenium complexes. [Pg.105]

The complex functions as the most suitable source of the tricarbonylruthe-nium unit in syntheses of tricarbonyl(7-diene)ruthenium complexes. Derivatives of 1,3-cyclohexadiene, 1,3-cycloheptadiene, cycloheptatriene, cyclooc-tatetraene, 2,4,6-cycloheptatrien-l-one, bicyclo[3.2. l]octa-2,6-diene, bicyclo-[3.2. l]octa-2,4-diene, and butadiene have been prepared by displacement of 1,5-cyclooctadiene. [Pg.106]

The significant potential of the ruthenium complex 65 was further underlined in the catalytic asymmetric ring-opening/cross metathesis of the cyclic alkene 70 (Scheme 44). This transformation is catalyzed by 5% mol of 65 at room temperature, in air, and with undistilled and nondegassed THF to deliver the corresponding diene 71 in 96% ee and 66% isolated yield. In standard conditions (distilled and degassed THF), the alkene 70 reacts in 75 min to give the diene in 95% ee and 76% yield, with only 0.5 mol % of catalyst. [Pg.219]

As invented by Wender,196,197 a variant of the second transformation can take place if the alkene partner is substituted by a participating group such as a strained cyclopropyl or a cyclobutanone (in the case of a 1,6-diene).198 The whole process, which mainly relies on the use of rhodium or ruthenium complexes,1 9 results in the formal... [Pg.325]

Fig. 2. Diene 64, the cyclized product 65 and the alkylidene ruthenium complex 66... Fig. 2. Diene 64, the cyclized product 65 and the alkylidene ruthenium complex 66...
Intermolecular enyne metathesis has recently been developed using ethylene gas as the alkene [20]. The plan is shown in Scheme 10. In this reaction,benzyli-dene carbene complex 52b, which is commercially available [16b], reacts with ethylene to give ruthenacyclobutane 73. This then converts into methylene ruthenium complex 57, which is the real catalyst in this reaction. It reacts with the alkyne intermolecularly to produce ruthenacyclobutene 74, which is converted into vinyl ruthenium carbene complex 75. It must react with ethylene, not with the alkyne, to produce ruthenacyclobutane 76 via [2+2] cycloaddition. Then it gives diene 72, and methylene ruthenium complex 57 would be regenerated. If the methylene ruthenium complex 57 reacts with ethylene, ruthenacyclobutane 77 would be formed. However, this process is a so-called non-productive process, and it returns to ethylene and 57. The reaction was carried out in CH2Cl2 un-... [Pg.156]

Ruthenium complexes are active hydrogenation catalysts for the reduction of dienes to monoenes. Both zerovalent and divalent ruthenium complexes containing various (alkene, diene and phosphine) ligands have been employed as catalysts that have met with different degrees of success. [Pg.400]

Ruthenium complexes B also undergo fast reaction with terminal alkenes, but only slow or no reaction with internal alkenes. Sterically demanding olefins such as, e.g., 3,3-dimethyl-l-butene, or conjugated or cumulated dienes cannot be metathesized with complexes B. These catalysts generally have a higher tendency to form cyclic oligomers from dienes than do molybdenum-based catalysts. With enol ethers and enamines irreversible formation of catalytically inactive complexes occurs [582] (see Section 2.1.9). Isomerization of allyl ethers to enol ethers has been observed with complexes B [582]. [Pg.144]

More synthetic interest is generated by the potentially very useful hydration of dienes. As shown on Scheme 9.6, methylethylketone (MEK) can be produced from the relatively cheap and easily available 1,3-butadiene with combined catalysis by an acid and a transition metal catalyst. Ruthenium complexes of several N-N chelating Hgands (mostly of the phenanthroline and bipyridine type) were found active for this transformation in the presence of Bronsted acids with weakly coordinating anions, typically p-toluenesulfonic acid, TsOH [18,19]. In favourable cases 90 % yield of MEK, based on butadiene, could be obtained. [Pg.223]

Electrocydization is another major mode of reaction utilizing the vinylidene complexes of Group 6 metals. It should be noted that the first example of this type of reaction was reported by Merlic et al. using a ruthenium complex employing nonaromatic diene-yne substrates [26]. [Pg.178]

Actually, applications of indenylidene-ruthenium complexes for alkene metathesis were reported before, at a time when the action mode of their ruthenium allenylidene precursors was not known. These complexes catalyzed a variety of RCM reactions of dienes and enynes [31, 32, 47] (see Section 8.2.2). [Pg.268]

Expanding on the encapsulation of organometallic guests, half-sandwich complexes of the form CpRu(q -diene)(H2O) were encapsulated in 1 [32]. When the diene portion of the half sandwich complex is unsymmetrically substituted, the ruthenium atom becomes a chiral center. Addition of CpRu(2-ethylbutadiene) (H2O) (4) to 1 revealed the existence of two diastereomers. Encapsulation of these racemic ruthenium complexes in racemic 1 leads to diastereomeric pairs of enantiomeric host-guest complexes (A/R, A/S, A/R, A/S) (Figure 7.3). However, chiral discrimination was not observed with the diastereomeric ratio (d.r.) being 50 50. [Pg.168]

The stereoselective synthesis of 1,4-disubstituted-l,3-dienes proceeds by head-to-head oxidative coupling of two alkynes with formation of an isolable metallacyclic biscarbene ruthenium complex [23], as shown in Scheme 6. Several key experiments involving labeled reagents and stoichiometric reactions and theoretical studies support the formation of a mixed Fischer-Schrock-type biscarbene complex which undergoes protonation at one carbene carbon atom whereas the other becomes accessible to nucleophilic addition of the carboxylate anion (Scheme 6) [23]. [Pg.68]

Several related examples of transition metal-catalyzed addition of C-H bonds in ketones to olefins have been reported (Table 2) [11-14]. The alkylation of diterpenoid 6 with olefins giving 7 proceeds with the aid of Ru(H)2(CO)(PPh3)3 (A) or Ru(CO)2(PPh3)3 (B) as catalyst [11], Ruthenium complex C, Ru(H)2(H2)(CO) (PCy3)2, has catalytic activity in the reaction of benzophenone with ethylene at room temperature [12]. The alkylation of phenyl 3-pyridyl ketone 8 proceeds with A as catalyst [13], Alkylation occurs selectively at the pyridine ring. Application of this C-H/olefin coupling to polymer chemistry using ce,co-dienes such as 1,1,3,3-tetramethyl-l,3-divinyldisiloxane 11 has been reported [14]. [Pg.170]

Along with diene and diyne metathesis, ene-yne metathesis has also been employed to form macrocycles. This type of metathesis is performed with the catalysts used for olefin metathesis, and the yields are improved in the presence of ethylene, which forms the highly reactive [Ru]=CH2 species. Shair and coworkers took advantage of this reaction twice in the course of their total synthesis of longithorone A [40]. When ene-ynes 51 and 52 are treated with ruthenium complex G1 under an atmosphere of... [Pg.45]


See other pages where Diene ruthenium complexes is mentioned: [Pg.401]    [Pg.352]    [Pg.378]    [Pg.352]    [Pg.378]    [Pg.394]    [Pg.394]    [Pg.401]    [Pg.352]    [Pg.378]    [Pg.352]    [Pg.378]    [Pg.394]    [Pg.394]    [Pg.274]    [Pg.320]    [Pg.452]    [Pg.586]    [Pg.154]    [Pg.639]    [Pg.869]    [Pg.717]    [Pg.898]    [Pg.69]    [Pg.138]    [Pg.674]    [Pg.616]    [Pg.181]    [Pg.176]    [Pg.406]   
See also in sourсe #XX -- [ Pg.217 , Pg.218 ]




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Complex diene

Conjugated diene complexes hydroacylation of, ruthenium-catalysed

Cycloocta-1,5-diene complexes ruthenium

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