First resolution of a linear chelating tetra(tertiary phosphine): resolution and absolute configurations of enantiomers of (R*,R*)-(±)-1,1,4,7,10,10-hexaphenyl-1,4,7,10-tetraphosphadecane

Abstract

The important and commercially available linear tetra(tertiary phosphine) (R*,R*)-(+.)/ ( R* , S* ) -P h 2PC H2C H2 P( P h ) CH2CH P( P h ) C H 2C H2 PP h2 has bee n se pa rated i n to d i aste reo i so m e rs a n d the ( R* , F )-(& )diastereoisomer resolved by the method of metal complexation giving the first optically active tetra(tertiary phosph ine).

Transformation of organic molecules on the low‐valent {M(Ph2PCH2CH2PPh2)2} moiety derived from trans‐[M(N2)2(Ph2PCH2CH2PPh2)2] or related complexes (M = MO, W)

“…In these reactions, stereochemistry of L is completely controlled, forming only a meso ‐form. It should be noted that stereoselective preparation of meso ‐ or rac ‐isomers of linear tetraphosphines has seldom been achieved 112–114…”

Completely stereoselective synthesis of a chiral tetra(tertiary phosphine). Crystal and molecular structure of [OC-6-22-(R*,R*)]-(±)-dichloro{1,2-bis[(2-dimethylphosphinophenyl)methylphosphino]benzene-P,P ′,P ″,P ‴}cobalt(III) hexafluorophosphate †

“…In addition, the (R*,R*) form of tetraphos has been successfully resolved by the method of metal complexation. 4 To date, however, there has been no report of a stereoselective synthesis of a linear tetra(tertiary phosphine). This is an important consideration if ligands of this type are to be investigated as potential chiral auxiliaries in asymmetric synthesis.…”

Stereoselective synthesis of chiral multidentate ligands with As2NP or As4P donor atoms *

“…2 The compounds 'tetars', and very recently, 'tetraphos', have also been successfully resolved. 8, 10 Optically pure (S P ,S P )-'tetraphos' was subsequently shown spontaneously to self-assemble into a homochiral double helix and side-by-side helix conformers of a doublestranded tetra(tertiary phosphine)disilver() complex. 11 Of these chiral compounds, only the racemic form of 'qars' was found to co-ordinate to cobalt() to give the cis-α diastereomer exclusively.…”