845821-92-3

Upstream product

• 342-23-4 bis(fluorophenyl)methanone 
• 15475-27-1 potassium diphenylphosphine 
• 13102-33-5 2,2'-dimethoxybenzophenone 
• 835-11-0 2,2'-dihydroxybenzophenone 
• 578-57-4 2-bromoanisole 
• 845821-95-6 bis(2-trifluoromethylsulfonyloxyphenyl)methanone 
• 829-85-6 diphenylphosphane 
• 77464-21-2 2-methoxy-α-(2-methoxyphenyl)benzenemethanol 
• 135-02-4 ortho-anisaldehyde 
• 583-55-1 1-Bromo-2-iodobenzene 
• 79-44-7 N,N-Dimethylcarbamoyl chloride 
• 62336-24-7 (2-bromophenyl)diphenylphosphane 

Downstream Products

• 54086-38-3 10-Phenyl-9,10-dihydro-10-λ⁵-acridophosphin-9,10-dion 

Relevant academic research and scientific papers

Enhanced Catalytic Activity of Nickel Complexes of an Adaptive Diphosphine-Benzophenone Ligand in Alkyne Cyclotrimerization

Adaptive ligands, which can adapt their coordination mode to the electronic structure of various catalytic intermediates, offer the potential to develop improved homogeneous catalysts in terms of activity and selectivity. 2,2′-Diphosphinobenzophenones have previously been shown to act as adaptive ligands, the central ketone moiety preferentially coordinating reduced metal centers. Herein, the utility of this scaffold in nickel-catalyzed alkyne cyclotrimerization is investigated. The complex [(p-tolL1)Ni(BPI)] (p-tolL1 = 2,2′-bis(di(para-tolyl)phosphino)-benzophenone; BPI = benzophenone imine) is an active catalyst in the [2 + 2 + 2] cyclotrimerization of terminal alkynes, selectively affording 1,2,4-substituted benzenes from terminal alkynes. In particular, this catalyst outperforms closely related bi- and tridentate phosphine-based Ni catalysts. This suggests a reaction pathway involving a hemilabile interaction of the C-O unit with the nickel center. This is further borne out by a comparative study of the observed resting states and DFT calculations.

Coordination of a Diphosphine-Ketone Ligand to Ni(0), Ni(I), and Ni(II): Reduction-Induced Coordination

The coordination chemistry of the diphosphine-ketone ligand 2,2′-bis(diphenylphosphino)benzophenone (Phdpbp) with nickel is reported. The ketone moiety does not bind to Ni(II) in the complex (Phdpbp)NiCl2, whereas reduction to Ni(I) or Ni(0) induces η2(C,O) coordination of the ketone to form the pseudotetrahedral complexes (Phdpbp)NiCl and (Phdpbp)Ni(PPh3). DFT calculations indicate that the metal-ketone bond is dominated by π back-donation; hence, Phdpbp functions as a hemilabile acceptor ligand in this series of complexes. (Chemical Equation Presented).

Complete chiral induction from enantiopure 1,2-diamines to benzophenone-based achiral bisphosphane ligands in noyori-type RuII catalysts

We report the design and synthesis of a novel class of RuII catalysts (3) composed of achiral benzophenone-based bisphosphane ligands and enantiopure 1,2-diamines for the asymmetric hydrogenation of aryl ketones. The developed catalysts show excellent enantioselectivities (up to 97 % ee) and activities (up to S/C = 10,000) in the hydrogenation of a variety of aromatic ketones. Complete chiral induction from the enantiopure 1,2-diamine to the achiral bisphosphane ligand was observed. The coordination of the C=O moiety in 3 to the cationic RuII center is considered to be of key importance in providing a higher thermodynamic and kinetic rotation barrier for the flexible bisphosphane ligand, resulting in the preferential formation of only one diastereomer, and thus explaining the high enantioselectivity of the catalyst. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.

NOVEL TRANSITION METAL COMPLEX AND PROCESS FOR PRODUCING OPTICALLY ACTIVE ALCOHOL WITH THE COMPLEX

A novel transition metal complex, preferably a ruthenium-phosphine complex or rhodium-phosphine complex, which is effectively usable in various asymmetric syntheses and, in particular, is more effectively usable in the asymmetric hydrogenation of various ketones; and a novel process for producing an optically active alcohol with the complex. The novel transition metal complex includes a ligand obtained by introducing a diarylphosphino group into each of the 2- and 2'-positions of diphenyl ether, benzophenone, benzhydrol, or the like. It preferably further includes an optically active 1,2-diphenylethylenediamine coordinated thereto. The complex preferably is a novel diphosphine-ruthenium-optically active diamine complex or diphosphine-rhodium-optically active diamine complex. The process comprises using the complex as an asymmetric hydrogenation catalyst to conduct the asymmetric hydrogenation of a ketone compound to thereby obtain an optically active alcohol in a high optical purity and a high yield.