Alkylation ruthenium chloride

In terms of economical synthetic approaches to indoles, the synthesis of this heterocycle from anilines and trialkylammonium chlorides was effected in an aqueous medium (H20-dioxane) at 180°C in the presence of a catalytic amount of ruthenium(III) chloride hydrate and triphenylphosphine together with tin(II)chloride <00TL1811>. Muchowski devised a novel synthetic route to indole-4-carboxaldehydes and 4-acetylindoles 86 via hydrolytic cleavage of W-alkyl-5-aminoisoquinolinium salts 85 to homophthaldehyde derivatives upon heating in a two phase alkyl acetate-water system containing an excess of a 2 1 sodium bisulfite-sodium sulfite mixture <00JHC1293>. 

The ruthenium atom is the target for electrophilic attack in reactions <90JOM(395)27> of (333) with a number of alkylating reagents, such as trimethylgermyl chloride (Scheme 33) or ethylene dibromide. 

Reaction of perfluoroalkanesulfonyl chlorides with aromatic compounds in the presence of dichloro bis(tnphenylphosphine)ruthenium (II) gives perfluoro alkylated products [162] (equation 139)... 

This type of receptor is represented by compounds 16a,b bearing ruthenium ) bipyridine moieties. Both calixarenes [18] exhibit 1 1 binding of chloride and bromide anions (DMSO-d6), and they are especially suitable for the complexation of H2POj (X16a=2.8-104 M-1 K16b=5.2 103 M"1). On the other hand, if we compare these results with those for similar non-calixarene receptors, where the bipyridine unit is substituted by alkyl, aryl or ethylene glycol substituents, the introduction of calixarene does not bring any substantially new features into the complexation abilities of these derivatives. As shown by X-ray analysis, the anion is encapsulated within the cavity formed by amidic functions with the contributions of CH...anion interactions from the bipyridine unit. 

Methyl />-tolyl sulfone has been prepared by oxidation of methyl 7>-tolyl sulfide with hydrogen peroxide 4 r or ruthenium tetroxide,6 by alkylation of sodium -toluenesullinate with methyl iodide 7,8 or with methyl potassium sulfate,9 by decarboxylation of -tolylsulfonylacetic acid,7 by thermal decomposition of tetramethylammonium -toluenesulfinate,10 by reaction of cw-bis-(%tolylsulfonvl)-ethene with sodium hydroxide (low yield),11 by the reaction of methanesulfonyl chloride with toluene in the presence of aluminum chloride (mixture of isomers),12 by... 

The main methodologies developed until now for enantioselective oxidation of sulfides are effective only in the oxidation of alkyl aryl sulfoxides. Dialkyl sulfoxides on the other hand are generally oxidized with only poor selectivity. In an attempt to solve this problem, Schenk s group69 recently reported a stereoselective oxidation of metal-coordinated thioethers with DMD. The prochiral thioether is first coordinated to a chiral ruthenium complex by reaction with the chloride complexes [CpRu[(S,S)-chiraphos]Cl], 36. Diastereoselective oxygen transfer from DMD produces the corresponding sulfoxides in high yield and selectivity. The chiral sulfoxides 37 are liberated from the complexes by treatment with sodium iodide. Several o.p. aryl methyl sulfoxides have been obtained by this method in moderate to high ee (Scheme 12). 

H2-labelled thioridazine 56 (the phenothiazine-type antipsychotic agent) has been obtained recently39 for metabolic and pharmacokinetic studies by a new route (equation 16) from 2-(2-hydroxyethyl)piperidine 57. The key steps in this sequence of reactions involve ruthenium tetroxide oxidation of the 7V,0-diacetylated starting material 58 and subsequent lithium aluminium deuteride reduction of the 2-(2-acetoxyethyl)-6-piper-idinone (59, R = Ac). Treatment of 60 with thionyl chloride produced 2-(2-chloroethyl)-l-methyl[6,6-2H2]piperidine which, on N(10)-alkylation of 2-methylthio-10i/-phenothia-zine, yielded 56. For each of the seven steps in the conversion of 57 to 56 the yield has been at least 76%40. 

The chiral octanediol in turn is converted into the corresponding cyclic sulfate by reaction with thionyl chloride and subsequent oxidation with sodium periodate and a catalytic amount of ruthenium(ni) chloride (0.1 mol%) (eq 2). In the final step, 1,2-diphosphinobenzene is lithiated by treatment with n-butyllithium (n-BuLi 2 equiv, 1.6 mol% in hexane) followed by the addition of the (3R,6R)-octane-3,6-diol cyclic sulfate (2 equiv) and a further addition of 2.2 equiv of n-BuLi. (5,5)-Ethyl-DuPHOS is obtained in a yield of over 70% [78% yield was described for the (R,R)-enantiomer by an analogous method ]. In addition to (5,5)-ethyl-DuPHOS, a variety of related bisphospholanes either linked by an ethylene bridge, or bearing other 2,5-alkyl substituents, or with opposite configuration have been prepared by this methodology. ... 

Kinetic resolution of secondary alcohols is performed by asymmetric oxidation using an optically active (nitroso)(salen)ruthenium(II) chloride 12 (Eq. 3.14) [48]. The ruthenium catalyst 12 is also effective for asymmetric imidation of alkyl aryl sulfide [48c]. 

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