512789-26-3Relevant articles and documents
Regio- and Enantioselective Allylation of Phenols via Decarboxylative Allylic Etherification of Allyl Aryl Carbonates Catalyzed by (Cyclopentadienyl)ruthenium(II) Complexes and Pyridine-Hydrazone Ligands
Egger, Léo,Tortoreto, Cecilia,Achard, Thierry,Monge, David,Ros, Abel,Fernández, Rosario,Lassaletta, José M.,Lacour, Jér?me
, p. 3325 - 3331 (2015/11/03)
(Cyclopentadienyl)tris(acetonitrile)ruthenium hexafluorophosphate [CpRu(CH3CN)3][PF6] in combination with pyridine-hydrazone ligands efficiently catalyzes the asymmetric decarboxylative allylic rearrangement of allyl aryl carbonates. Formation of C-O bonds with high regio- and enantioselectivity ratios (up to 95:5 and 98% ee) is obtained. Good stereocontrol of the pseudotetrahedral geometry of the CpRu moiety is achieved by the hydrazone ligand and its "electron-poor" nature is evidenced through the epimerization of the hexacoordinated TRISPHAT-N anion.
From precursor to catalyst: The involvement of [Ru(η5- Cp*)Cl2]2 in highly branch selective allylic etherification of cinnamyl chlorides
Siddappa, Ravi Kumara Guralamatta,Chang, Chih-Wei,Chein, Rong-Jie
supporting information, p. 1031 - 1035 (2014/02/14)
(RuCp*Cl2)2, a general entry into Cp*Ru sandwich and half-sandwich chemistry was first used as a precatalyst in allylic etherification of cinnamyl chlorides with up to 98:2 regioselectivity (19 examples). Both the solvent effect and the exsiccant reaction condition are crucial to the reactivity and selectivity. Preliminary mechanism studies and the demonstration of Fluoxetine synthesis were presented in this work as well.
Imidazolium-oxazoline salts in ruthenium-catalyzed allylic substitution and cross metathesis of formed branched isomers
Ammar, Hamed Ben,Hassine, Bechir Ben,Fischmeister, Cedric,Dixneuf, Pierre H.,Bruneau, Christian
experimental part, p. 4752 - 4756 (2011/02/28)
Imidazolium-oxazoline chlorides have been prepared from chloroacetonitrile and used to generate bidentate mixed NHC-oxazoline ligands for ruthenium-catalyzed substitution of cinnamyl chloride by phenols. These ligands associated to [RuCp*(MeCN)3][PF6] promote allylic substitution reactions at room temperature with high regioselectivity in favour of the branched isomers giving terminal alkenes. These allylic ethers have been involved in further ruthenium-catalyzed cross metathesis reactions with electron-deficient olefins to give unsaturated esters and aldehydes. NHC-oxazoline ligands associated to the Cp*RuII moiety generate catalysts that orientate the nucleophilic allylic substitution of cinnamyl chloride by phenols towards the regioselective formation of branched products, which, on reaction with Hoveyda(II) catalyst, lead to cross metathesis, and unsaturated functional compounds.