131516-15-9Relevant articles and documents
Palladium-catalyzed asymmetric intermolecular arylation of cyclic or acyclic alkenes using phosphinite-oxazoline ligands derived from D-glucosamine
Yonehara, Koji,Mori, Kenji,Hashizume, Tomohiro,Chung, Kang-Go,Ohe, Kouichi,Uemura, Sakae
, p. 40 - 49 (2000)
Chiral phosphinite-oxazolines, 2-alkyl- or 2-aryl-4,5-(4,6-O-benzylidene-3-O-(diphenylphosphino)-1,2-di-deoxy-a-D- glucopyra-nosyl)-[2,1-d]-2-oxazolines 1a-f derived from D-glucosamine hydrochloride, are revealed to work as effective P,N-bidentate ligands in the palladium-catalyzed enantioselective arylation of 2,3-dihydrofuran to give 2-aryl-2,5-dihydrofuran selectively in high yield with up to 96% ee. The first asymmetric phenylation reaction of trans and cis-crotyl alcohols as acyclic alkenes with iodobenzene is also carried out to afford 3-phenylbutanal in moderate chemical yield with up to 17% ee. The complex [PdCl2(1b)] is newly prepared and its structure is characterized by X-ray crystallography. Structures of the new complex [(p-MeO2CC6H4)PdI(1a)] (8) and its cationic complex [(p-MeO2CC6H4)Pd(1a)]+OTf - (9) are also elucidated on the basis of 1H-, 13C-, and 31P-NMR spectra, p-MeO2CC6H4 moiety on the palladium being located trans to the nitrogen of 1a. This configuration might be responsible for an enantiofacial discrimination of 2,3-dihydrofuran to produce (R) isomer predominantly. The stoichiometric reaction of [PhPd(1f)]+OTf- (11) with 2,3-dihydrofuran has provided the mechanistic aspect for the arylation using P,N-ligands, in which the base-promoted deprotonation at β-position leading to an alkene(2-aryl-2,5-dihydrofuran)-palladium(0) complex has been shown to be an important step for the selective formation of the product.
Asymmetric intermolecular heck reaction of aryl halides
Wu, Chunlin,Zhou, Jianrong
supporting information, p. 650 - 652 (2014/02/14)
The asymmetric intermolecular Heck reaction has been limited to aryl and vinyl triflates. Herein, we extend the reaction to aryl and vinyl bromides. Various cyclic olefins coupled with high enantioselectivity. Only bisphosphine oxides on a spiro backbone formed highly stereoselective Pd catalysts. The use of alcoholic solvents and alkylammonium salts were essential to promote halide dissociation from neutral arylpalladium complexes.
Palladium-catalyzed asymmetric Heck arylation of 2,3-dihydrofuran-effect of prolinate salts
Morel, Adam,Silarska, Ewelina,Trzeciak, Anna M.,Pernak, Juliusz
, p. 1215 - 1222 (2013/02/23)
Chiral ionic liquids (CILs) containing l-prolinate and l-lactate anions and non-chiral quaternary ammonium cations were employed in the palladium catalyzed enantioselective Heck arylation of 2,3-dihydrofuran with aryl iodides (iodobenzene, 4-iodotoluene, 2-iodoanisole, 4-iodoanisole, 4-iodoacetophenone). In all the reactions 2-aryl-2,3-dihydrofuran (3) was obtained as the main product with the yield up to 52% at the total conversion reaching 83%. Product 3, 2-phenyl-2,3-dihydrofuran, was obtained with excellent enantioselectivity (>99% ee) in a 6 h reaction with tetrabutylammonium l-prolinate. In the proposed homogeneous reaction Pd(0) nanoparticles are considered as a resting state of the catalyst and a source of soluble palladium species catalyzing the Heck reaction. The yield and stereoselectivity of the Heck reaction are strongly influenced by the kind of non-chiral cations present in CILs. The Royal Society of Chemistry 2013.
