ISSN:
0009-2940
Keywords:
Lithiation
;
P ligands
;
NMR spectroscopy
;
Molecular structure
;
Hydrogenations
;
Hydroformylations
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
A facile synthesis of 2′-phosphanyl-1,1′-biphenyl- and 2′-phosphanyl-1,1′ -binaphthyl-2-ols and their silyl ethers has been developed, consisting of electron-transfer-catalyzed ring-opening of dibenzofuran and dinaphthofuran, respectively, subsequent reaction with chlorophosphanes, and work-up with acetic acid or ClSiMe3. Studies of the molecular and crystal structures reveals the presence of P - H - O bridging bonds in the more basic tBuPhP derivative and a nearly perpendicular arrangement of the aryl planes in the biphenyl derivatives. The barrier to rotation of the aryl planes about the C-C axis was determined by NMR in the case of the P-asymmetric derivative 3d, using the appearence of diastereoisomers by atropisomerism and P-asymmetry. Comparative screening tests of the title compounds, phosphanyl phenols and phosphanylnaphthols in homogeneous Rh-catalyzed reactions demonstrate catalytic activity in hydroformylation reactions and superior properties of the biphenyl- and binaphthyl-2-ol derivatives in relation to other P-O ligands.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19971301118
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