(2-Hydroxyphenyl)diphenylphosphine

o‐Hydroxyarylphosphanes: Strategies for Syntheses of Configurationally Stable, Electronically and Sterically Tunable Ambiphiles with Multiple Applications

“…The latter were obtained from (R)-BINOL by consecutive treatment with ArCH 2 Br (K 2 CO 3 ), NaH and MOMCl to give 11 and subsequent o-lithiation and phosphanylation (Scheme 4c). Further lithiation of the OCH 2 Ar group with iBuLi resulted in a diastereoselective [1,2]-Wittig-rearrangement. Quenching with aqueous NH 4 Cl gave 2'-CH(OH)Ar derivatives 13 (Ar-BINMOL-Phos), used for Zn-mediated asymmetric additions of aryl alkynes to aldehydes.…”

“…[1] A special class with tremendous potential for multifunctional and steric variations and versatile applications are o-hydroxyarylphosphanes (Figure 1). The most frequently used compound of type 1 is probably still 2-diphenylphosphanylphenol 1 Ph , [2] but a multitude of new representatives and types of the title compounds, reported in the last ca. 40 years, allows tuning of steric and electronic properties by variation of substituents.…”

“…For borderline compounds the configuration may be reversible solvent-(benzene cis, CDCl 3 trans) or, as shown for VII, conditiondependent (crystalline cis or dissolved trans), [27] indicating hemilabile behavior. [28] Cationic o-phosphanylphenol Ni or Pd complexes VIIIa,b with SbF 6 À anion, active but unselective catalysts for conversion of ethylene to dimers and lower oligomers, might form M II chelates with (P,OH) ligands, as shown for single crystals with hydrogen-bonded THF of the Pdprecursor VIIIb (PdÀ O 2.161 (2), H…O THF 1.662 Å, < DHA 176.72). In the solid state these compounds decompose slowly (with BF 4…”