134273-44-2Relevant academic research and scientific papers
Stereoselective Addition of Diphenylphosphine: meso- and rac-1,2-Diphenyl-1,2-bis(diphenylphosphino)ethane and their Group 6 Metal Tetracarbonyl Complexes. Crystal Structures of the Molybdenum Derivatives
Bookham, Jonathan L.,McFarlane, William,Thornton-Pett, Mark,Jones, Simon
, p. 3621 - 3627 (1990)
The addition of diphenylphosphine, PPh2H, to diphenylethyne in the presence of KOBut has been followed by 31P n.m.r. spectroscopy, and according to the reaction conditions can yield cis, (2) or trans, (3), 1,2-diphenyl(diphenylphosphino)ethene
Stereoselective addition of diphenylphosphine to substituted diphenylethynes: Synthetic, NMR and X-ray crystallographic studies
Bookham, Jonathan L.,Smithies, Darren M.,Wright, Anna,Thornton-Pett, Mark,McFarlane, William
, p. 811 - 818 (2007/10/03)
The base-catalysed addition of diphenylphosphine to the substituted diphenylethynes RC≡CR′ (R = Ph, R′ = Ph, o-tolyl, m-tolyl or 2-biphenyl; R = m-tolyl, R′ = o-tolyl or m-tolyl) yielded Ph2PC(R)=CHR′ and/or Ph2PCH(R)CH(R′)PPh2. Proton, 13C, 13P and two-dimensional rotating frame Overhauser enhancement 1H NMR spectra have been used to determine the stereochemical pathways of the reactions and the stereochemistry of the products. In general the more hindered alkynes undergo monoaddition ultimately to yield phosphinoalkenes with the Ph2P attached to the carbon bearing the least bulky substituent and cis to the olefinic proton, while for the less hindered alkynes the trans isomer is formed initially and this then reacts further to give mesolerythro-diphosphinoalkanes. Bis(o-tolyl)ethyne does not react with Ph2PH under the same conditions. Crystal structures were determined for E- and Z-Ph2P(Ph)C=CHPh and show distortions of interbond angles consistent with the pattern of strain implied by the foregoing reactions. The sulfides of the phosphinoalkenes and the Mo(CO)4 complexes of the diphosphinoalkanes were also prepared and their 1H, 13C and 31P NMR spectra recorded. In several cases the pattern of 13CO NMR signals for the complexes was used unambiguously to determine the stereochemistry of the parent diphosphines.
The Mechanism of Asymmetric Hydrogenation. Chiral Bis(diphenylphosphino)-α-phenylalkane Complexes in Catalytic and Structural Studies
Brown, John M.,Murrer, Barry A.
, p. 489 - 498 (2007/10/02)
(R)-1,2-Bis(diphenylphosphino)phenylethane has been synthesised in good overall yield from (S)-mandelic acid ; its cationic rhodium(I) solvated complex has been shown to be effective in catalytic asymmetric hydrogenation with optical yields of up to 88percent having been observed.The n.m.r. spectra of complexes of this phosphine are discussed.Racemic (R*,R*)-1,3-bis(diphenylphosphino)-1,3-diphenylpropane and (R*,R*)-1,4-bis(diphenylphosphino)-1,4-diphenylbutane have been prepared.These form a range of rhodium complexes with dehydroamino-acids whose structures may be assigned on the basis of characteristic n.m.r.P-Rh and P-P coupling constants.
