106865-17-2

Upstream product

• 41593-58-2 diphenylphosphineborane 
• 829-85-6 diphenylphosphane 
• 1383686-38-1 (2-iodophenyl)-diphenylphosphine borane 
• 603-35-0 triphenylphosphine 
• 615-42-9 1,2-Diiodobenzene 
• 17154-34-6 (trimethylsilyl)diphenylphosphine 

Downstream Products

• 503859-68-5 CH₃C₆H₄SO(C₅H₃)Fe(C₅H₅)(C₆H₄)P(C₆H₅)2 
• 885702-66-9 diphenyl-(2-trimethylsilyl-phenyl)phosphine 
• 88652-75-9 2-iodophenyldiphenylphosphine oxide 

Relevant academic research and scientific papers

P-CHIROGENIC ORGANOPHOSPHORUS COMPOUNDS

The present invention relates to novel P-chirogenic organophosphorus compounds of general formula (I). The present invention also provides a process for the synthesis of said compounds of formula (I). The present invention also relates to intermediate products of general formulae (II), (III) and (IV), as shown below, which are involved in the synthesis of compounds (I). Further, the invention relates to metal complexes comprising compounds (I) as ligands. The novel compounds and complexes of the present invention are useful in asymmetric catalysis by transition metal complexes or organocatalysis, especially for asymmetric hydrogenation or allylation. Compounds of general formula (I) may useful as agrochemical and therapeutic substances, or as reagents or intermediates for fine chemistry.

Stereoselective synthesis of o-bromo (or iodo)aryl P-chirogenic phosphines based on aryne chemistry

The efficient synthesis of chiral or achiral tertiary phosphines bearing an o-bromo (or iodo)aryl substituent is described. The key step of this synthesis is based on the reaction of a secondary phosphine borane with the 1,2-dibromo (or diiodo)arene, owing to the formation in situ of an aryne species in the presence of n-butyllithium. When P-chirogenic secondary phosphine boranes were used, the corresponding o-halogeno-arylphosphine boranes were obtained without racemization in moderate to good yields and with ee up to 99%. The stereochemistry of the reaction, with complete retention of the configuration at the P atom, has been established by X-ray structures of P-chirogenic o-halogenophenyl phosphine borane complexes. The decomplexation of the borane was easily achieved without racemization using DABCO to obtain the free o-halogeno-arylphosphines in high yields.

Switching on and off metalation sites in triarylphosphines by manipulating substrate coordination

The inductive electron-withdrawing effect of the positively charged phosphorus atom in triarylphosphine-borane adducts is largely compensated by the steric congestion caused in its vicinity. Therefore, trihydro(triphenylphosphonio)borate reacts only sluggishly even with superbasic reagents and products derived from ortho-metalated intermediates by their trapping with electrophiles are formed only in poor yield. On the other hand, the borane adducts of (3-anisyl)diphenylphosphine and (3- fluorophenyl)diphenylphosphine can be readily deprotonated at the hetero- adjacent para position and converted into final products in high yields. The phosphorus-remote regioselectivity of these phosphine-borane zwitterions is complementary to that previously observed with the corresponding phosphine oxides.

Palladium-Catalyzed Coupling of Aryl Halides with (Trimethylstannyl)diphenylphosphine and (Trimethylsilyl)diphenylphosphine

The palladium-catalyzed reaction of aryl halides with either (trimethylsilyl)diphenylphosphine or (trimethylstannyl)diphenylphosphine gives aryldiphenylphosphines in good yields, under relatively mild conditions (50-70 deg C, benzene).The reaction tolerates a number of functional groups including methyl ethers, esters, ketones, nitriles, anilides, and certain halogens.The nitro and aldehyde groups as well as compounds containing groups such as amino and hydroxyl are not tolerated.