201011-35-0Relevant academic research and scientific papers
Customized Buchwald-Type Phosphines Bearing an "Inverted" Pyrimidinium Betaine as an Aryl Group Surrogate - Synthesis and Coordination Chemistry with Gold(I)
No?l-Duchesneau, Ludovik,Lugan, No?l,Lavigne, Guy,Labande, Agnès,César, Vincent
, p. 1752 - 1758 (2015)
A new ligand scaffold inspired by Buchwald-type phosphines is disclosed. Its design consists of the formal replacement of the distal aryl group of the original archetype by a pyrimidinium betaine connected to the o-phosphinophenyl moiety through the C-5 position of its malonate subunit. A productive synthetic pathway towards this phosphine is described along with its ability to coordinate to a gold(I) center. A weak bonding interaction between the metal center and the malonate group is observed in the solid state.
A dramatic switch of enantioselectivity in asymmetric heck reaction by benzylic substituents of ligands
Wu, Wen-Qiong,Peng, Qian,Dong, Da-Xuan,Hou, Xue-Long,Wu, Yun-Dong
scheme or table, p. 9717 - 9725 (2009/02/04)
A series of benzylic substituted P,N-ligands 1 and 2 have been synthesized. The Pd-complexes of these ligands show high catalytic activity and enantioselectivity in catalyzing the asymmetric Heck reaction. A dramatic switch in enantioselectivity is realized using ligands with and without substituents at the benzylic position of the ligand. Ligands 1 with H as the substituents offer products in (R)-configuration while ligands 2 with the methyl as substituents result in (S)-configuration products. In most cases high enantioselectivities are achieved. Density functional theory calculations on the reaction mechanism as well as X-ray analysis of 1a-PdCl2 and 2a-PdCl2 complexes provide a rational explanation for the above observations.
Synthesis of new chiral benzylically substituted P,N-ligands and their applications in the asymmetric Heck reaction
Hou, Xue-Long,Dong, Da Xuan,Yuan, Ke
, p. 2189 - 2191 (2007/10/03)
A series of new chiral P,N-ligands with substituents at the benzylic position has been prepared. Their high catalytic activity is shown in the Pd-catalyzed asymmetric Heck reaction and allylic substitution reaction.
Nucleophilic phosphanylation of fluoroaromatic compounds with carboxyl, carboxymethyl, and aminomethyl functionalities - An efficient synthetic route to amphiphilic arylphosphanes
Hingst, Martin,Tepper, Michael,Stelzer, Othmar
, p. 73 - 82 (2007/10/03)
Chiral- and multiply-carboxylated phosphanes and phosphanyl derivatives of benzoic and phthalic acids (1-9) are accessible in high yields by nucleophilic phosphanylation of potassium or lithium salts of commercially available fluorobenzoic and 3-fluorophthalic acids with Ph2PH, Ph2PK, PhPLi2, Ph(K)P-(CH2)3-P(K)Ph in superbasic media (DMSO/KOH) or in THF and DME. The hitherto unknown phosphanylphenylacetic acids (10-13) and phosphanylbenzylamines RR′P-C6H4-CH2-NH2 (14-19, R, R′ = H, Me, Ph) with unsubstituted amino groups were also synthesized by this method. The diphenylphosphanyl derivatives 14-16 (R, R′ = Ph) are accessible by an alternative method involving LiAlH4 reduction of the phosphanylbenzonitriles (20-22), which were obtained in high yields by nucleophilic phosphanylation of the corresponding fluoro- or chlorobenzonitriles. The novel bidentate phosphanylbenzonitrile 23 has also been obtained using this synthetic route. All compounds were completely characterized by elemental analysis, NMR spectroscopy, and mass spectrometry.
