Chiral hexacoordinated phosphates: From pioneering studies to modern uses in stereochemistry

Abstract

Chiral cationic molecular structures and supramolecular assemblies can be effectively analyzed, resolved and stereocontrolled through an asymmetric ion pairing with enantiopure hexacoordinated phosphate anions like TRISPHAT or BINPHAT. After an historical perspective on the development of these anionic reagents, this account describes their synthesis and their use as chiral NMR solvating, resolving and asymmetry-inducing reagents.

Taming the Cationic Beast: Novel Developments in the Synthesis and Application of Weakly Coordinating Anions

“…[163,164] Furthermore, despite the high toxicity of perfluoropinacole,t he [B(O 2 C 2 -(CF 3 ) 4 ) 2 ] À ion has received attention in the literature, predominantly in the area of lithium ion batteries. [158,168,169] Siu and Gates have reported the formation and solid-state structures of L 2 H[P(O 2 C 6 H 5 ) 3 ]( where L = DMSO or DMF) and the subsequent application for the protonolysis of the palladium-carbon bonds in Pd(Me) 2 -(dppe) (dppe = 1,2-bis(diphenylphosphino)ethane) to give the corresponding palladium salts. Although the parent catechol-based anion was reported in 1970, it has seen only limited use as aWCA because of its racemization in solution.…”

“…Although the parent catechol-based anion was reported in 1970, it has seen only limited use as aWCA because of its racemization in solution. [158,168,169] Siu and Gates have reported the formation and solid-state structures of L 2 H[P(O 2 C 6 H 5 ) 3 ]( where L = DMSO or DMF) and the subsequent application for the protonolysis of the palladium-carbon bonds in Pd(Me) 2 -(dppe) (dppe = 1,2-bis(diphenylphosphino)ethane) to give the corresponding palladium salts. [170] Thep reparation of the chlorinated analogue [P(O 2 C 6 Cl 4 ) 3 ] À ,e fficient resolution of the enantiomers,a nd demonstration of its configurational stability in solution at room temperature has led to agrowing usage of this class of anion.…”

“…2009 Chiral Anion-mediated Asymmetric Ion Pairing Chemistry [157] 2010 Chiral Hexacoordinated Phosphates:F rom Pioneering Studies to Modern Uses in Stereochemistry [158] 2011 Arylspiroboronate Esters:F rom Lithium Batteries to Wood PreservativestoC atalysis [159] 2011 Lithium-ionC onducting Electrolyte Salts for Lithium Batteries [50] 2014 Electrolytesand Interphases in Li-Ion Batteries and Beyond [55] Figure 6. Trisphat-type anions and oxalatoborates.…”

Absolute Configuration and Enantiodifferentiation of a Hemicryptophane Incorporating an Azaphosphatrane Moiety

“…28,29 In recent years, chiral hexacoordinated phosphorus TRISPHAT anion [30][31][32][33][34] has been shown to be valuable CSA for chiral cationic species (Fig. 28,29 In recent years, chiral hexacoordinated phosphorus TRISPHAT anion [30][31][32][33][34] has been shown to be valuable CSA for chiral cationic species (Fig.…”

Reaction of 6-bromo-2-hydroxy-4-tributylphosphonium naphthyl-1-ate with chlorobis(phenylenedioxy)spirophosphoranes

“…[1][2][3][4]. In this report, we first suggest to use the reaction of P(IV)-containing betaines, such as 6-bromo-2-hydroxy-4-tributylphosphonium naphthyl-1-ate I, with bis-(phenylenedioxy)chlorophosphoranes IIa-IIc in the synthesis of the P(VI)-derivatives.…”