40927-85-3

Upstream product

• 4559-70-0 Diphenylphosphine oxide 
• 110-00-9 furan 
• 2948-14-3 furan-2-carboxylic acid phenyl ester 

Relevant academic research and scientific papers

Mn-Catalyzed Electrooxidative Undirected C-H/P-H Cross-Coupling between Aromatics and Diphenyl Phosphine Oxides

C-P bonds are widely found in a great many bioactive compounds and functional molecules. Transition-metal-catalyzed dehydrogenative C-H/P-H cross-coupling plays a crucial part in C-P bond formation since it requires no pretreatment of substrates. Herein, we reported a Mn-catalyzed electrochemical intermolecular dehydrogenative cross-coupling between aryl C-H and diphenyl phosphine oxides. In undivided cells, a series of phosphorylation or diphosphorylation products could be obtained separately by adjusting the proportion of substrates. A catalytic amount of inexpensive Mn(II) salt was used, and no external chemical oxidants were needed in this process. A kinetic isotope effect experiment suggested that the C-H activation was not the rate-determining step.

Nickel-catalyzed C–P cross-coupling of (het)aryl tosylates with secondary phosphine oxides

A novel and convenient approach to the synthesis of various tertiary phosphine oxides via nickel-catalyzed cross-coupling of (het)aromatic tosylates with secondary phosphine oxides is developed. The reaction employs cheap nickel as the catalyst, 1-(2-(di-tert-butylphosphanyl)phenyl)-4-methoxypiperidine (L3) as the ligand, and pyridine as the base. This reaction produces the corresponding (het)aromatic phosphorus compounds in good to high yields. Moreover, four new tertiary phosphine oxides are reported in this process.

Decarbonylative C-P bond formation using aromatic esters and organophosphorus compounds

Ni-catalyzed C-P bond formation was achieved using aromatic esters as unconventional aryl sources. The key to success was the use of a thiophene-based diphosphine ligand (dcypt). Several aromatic esters including heteroaromatics can be coupled with phosphine oxides and phosphates, providing aryl phosphorus compounds. The synthetic utility of the method was demonstrated by application of the present protocol to the sequential coupling reactions.

Electronic properties of furyl substituents at phosphorus and their influence on 31P NMR chemical shifts

The electronic properties of 2-furyl and 3-furyl substituents attached to phosphanes and phosphonium salts were studied by means of IR spectroscopy and experimental and computational 31P NMR spectroscopy. The heteroaromatic systems proved to be electron withdrawing with respect to phenyl substituents. However, phosphorus atoms with attached furyl substituents are strongly shielded in NMR. The reason for this phenomenon was studied by solid state 31P MAS NMR experiments. The chemical shift tensor was extracted, and the orientation within the molecules was determined. The tensor component σ33, which is effected the most by furyl systems, is oriented perpendicular to the P-C bonds of the substituents. P-furyl bonds are shorter than P-phenyl bonds. We assume therefore a lower ground-state energy of the molecules, because of the electron withdrawing properties of the 2-furyl systems. The σpara component of the 31P NMR magnetic shielding is therefore smaller, which results in an overall increase of the magnetic shielding.

A Wittig reaction with 2-furyl substituents at the phosphorus atom: Improved (Z) selectivity and isolation of a stable oxaphosphetane intermediate

Wittig reactions with ylides bearing one, two or three 2-furyl groups directly bound to the phosphorus atom have been studied. Greatly improved (Z)-alkene selectivities of up to 98:2 could be observed if 2-furyl groups were present. Monitoring of the reactions by NMR spectroscopy revealed only oxaphosphetane intermediates, which became more stable with increasing number of 2-furyl substituents bound to the phosphorus atom. Oxaphosphetane 10d, with three furyl groups, was successfully isolated, and the results of a crystal structure analysis are presented. Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002.