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Asymmetric Synthesis and Configurational Stability of C 2 ‐Symmetric Hexacoordinated Phosphate Anions (TARPHATs) with Predetermined Chirality from Tartrate Esters
Author(s) -
Lacour Jérôme,
Londez Anne,
Tran DuyHien,
DesvergnesBreuil Valérie,
Constant Samuel,
Bernardinelli Gérald
Publication year - 2002
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/1522-2675(200205)85:5<1364::aid-hlca1364>3.0.co;2-q
Subject(s) - chemistry , tartrate , chirality (physics) , phosphate , axial chirality , stereochemistry , enantioselective synthesis , computational chemistry , stability (learning theory) , crystallography , organic chemistry , catalysis , chiral symmetry , physics , quantum mechanics , computer science , nambu–jona lasinio model , quark , machine learning
C 2 ‐Symmetric TARPHAT anions 5 made of a central P V atom, one tartrato (=dialkyl 2,3‐di(hydroxy‐ κO )butanedioato(2−)), and two tetrachloropyrocatecholato (=3,4,5,6‐tetrachlorobenzene‐1,2‐diolato(2−)‐ κO , κO ′) ligands can be easily prepared in decent to high yields (50–86%) as their dimethylammonium salt by using a one‐pot process and simple commercially available starting materials. The presence of the chiral tartrato ligands (usually (2 R ,3 R )) leads to the formation of diastereoisomeric anions (( Δ ,2 R ,3 R )/( Λ ,2 R ,3 R )). Decent to good control by the chiral ligands – under equilibration conditions – over the Λ or Δ configuration of the adducts was observed (d.r. 84 : 16 in CHCl 3 for the di( tert ‐butyl) tartrate derivative), the selectivity depending on the nature of the ester chains as well as on the solvent.