80317-71-1

Upstream product

• 1079-66-9 chloro-diphenylphosphine 
• 503818-00-6 (+/-)-8-bromo-2'-methoxy-1,1'-binaphthyl 
• 3401-47-6 1-bromo-2-methoxynaphthalene 
• 13922-41-3 1-Naphthylboronic acid 

Downstream Products

• 167417-60-9 3-Phenyl-[1,1']binaphthalenyl-2-ol 
• 93-04-9 2-Methoxynaphthalene 

Relevant academic research and scientific papers

Fine Tuning of Chiral Bis(N-heterocyclic carbene) Palladium Catalysts for Asymmetric Suzuki-Miyaura Cross-Coupling Reactions: Exploring the Ligand Modification

Novel chiral N,N′-bisaryl bis(NHC) ligand precursors H2[(S)-2]Cl2 on a spiro scaffold and H2[(S)-3b-g]Cl2 with a binaphthyl linkage were rationally designed and their cyclometalated cis-chelated NHC palladium complexes (S)-5, (S)-6, and (S)-7b-g have been synthesized and fully characterized. Complexes 6 and 7b were further confirmed by X-ray single-crystal analysis. Both complexes adopted a slightly distorted square planar geometry around the Pd(II) center. The structure of 6 consists of a rare dimeric arrangement incorporating two palladium(II) centers bonded through a short metal-metal bond (2.853(2) ?), indicating a PdII-PdII intramolecular interaction (?). These N,N′-bisaryl-bis(NHC)-Pd complexes together with N,N′-bisalkyl analogues {[(S)-1a-d]PdX2} (X = I, (S)-4a; X = Br, (S)-4b-d) have been used in the asymmetric aryl-aryl cross-coupling reactions of arylboronic acids and aryl halides. The enantioselectivity of the biaryl products was greatly improved within 24 h (up to 74% ee) when complexes 7a-g were used as catalysts. The results show that for these types of bis(NHC) palladium catalysts the structural characters of the chiral scaffolds play a decisive role in the enantioselectivities of cross-coupling reactions.

Pyridylalkylamine ligands and their palladium complexes: Structure and reactivity revisited by NMR

Pyridylmethylamines or pma are versatile platforms for different catalytic transformations. Five pma-ligands and their respective Pd complexes have been studied by liquid state NMR. By comparing 1H, 13C and 15N chemical shifts for each pma/pma-Pd couple, a general trend for the metallacycle atoms concerns variations of the electronic distribution at the pendant arm, especially at the nitrogen atom of the ligand. Moreover, the increase of the chemical shift of the pendant arm nitrogen atom from primary to tertiary amine is also related to the increase of crowding within the complex. This statement is in good agreement with X-ray data collected for several complexes. Catalytic results for the Suzuki-Miyaura reaction involving the pma-Pd complexes showed within this series that a sterically crowded and electron-rich ligand in the metallacycle was essential to reach the coupling product with a good selectivity. In this context, NMR study of chemical shifts of all active nuclei especially in the metallacycle could give a trend of reactivity in the studied family of pma-Pd complexes. Copyright

N-heterocyclic pyridylmethylamines: Synthesis, complexation, molecular structure, and application to asymmetric Suzuki-Miyaura and oxidative coupling reactions

The synthesis of N,N-bidentate ligands based on a π-deficient N-heterocyclic pyridylmethylamine core is described. The preparation and characterization of the corresponding N,N-ligand-palladium complexes in solution and the solid state are illustrated. Pd complexes showed a good yield and moderate catalytic activity (up to 40% ee) in the asymmetric Suzuki-Miyaura coupling reaction, leading to methoxybinaphthyl derivatives. The combination of N,N-pyridylmethylamines with cuprous iodide revealed effective catalytic systems in oxidative naphthol derivative coupling reactions, affording the corresponding binaphthyls in high yields and with enantioselectivities of up to 61%.

2,8'-Disubstituted-1,1'-Binaphthyls: A New Pattern in Chiral Ligands

The title binaphthyls 19 and 26, which are the positional isomers of 2-methoxy-2'-(diphenylphosphino)-1,1'-binaphthyl (MOP, 19) and 2-amino-2'-hydroxy-1,1'-binaphthyl (NOBIN, 26), have been synthesized by Suzuki coupling as the key step (10 + 15 -> 18), followed by functional group transformations, involving C-P and C-N bond formation (18 -> 19 and 18 -> 23). Racemic intermediate 22 was resolved by cocrystallization with N-benzylcinchonidinium chloride and the absolute configuration determined by X-ray crystallography. These novel binaphthyls are configurationally stable and, as such, potentially usable as chiral ligands in asymmetric reactions. Michael addition of the glycine-derived enolate 40 to methyl acrylate, carried out in the presence of (R)-(-)-27 as the chiral phase-transfer catalyst, afforded L-glutamic acid (S)-(+)-43 of 92% ee (after hydrolysis of the primary product).