General and Stereoselective Method for the Synthesis of Sterically Congested and Structurally Diverse P-Stereogenic Secondary Phosphine Oxides

Abstract

A general and efficient method for the synthesis of bulky and structurally diverse P-stereogenic chiral secondary phosphine oxides (SPOs) by using readily available chiral amino alcohol templates is described. These chiral SPOs could be used as chiral building blocks for the synthesis of difficult-to-access bulky P-stereogenic phosphine compounds or ligands for organic catalysis.

Synthesis of optically active tertiary phosphine oxides: A historical overview and the latest advances

“…A series of secondary phosphine oxides 31 was used for the synthesis of tertiary phosphine oxides 32 by the reaction with 2‐bromopyridine, catalyzed by Pd 2 (dba) 3 (Scheme ) . In turn, optically pure secondary phosphine oxides 31 were synthesized using optically pure sulfonamide derivatives of (1 R ,2 S )‐norephedrine 28 or (1 S ,2 R )‐aminoindanol 29 .…”

The resolution of acyclic P‐stereogenic phosphine oxides via the formation of diastereomeric complexes: A case study on ethyl‐(2‐methylphenyl)‐phenylphosphine oxide

“…In the study of the resolving agents, the stirring of the solid diastereomers in a given solvent mixture was the purification method used. 21,44,78,79 Besides the purification of diastereomers used earlier ( Table 2, entry 2), the repeated resolution according to the half equivalent or the equivalent method, or the recrystallization of the enantiomeric mixtures was also considered as an option.…”

“…To the best of our knowledge, despite the simplicity of this method, only a few examples can be found in the literature, when the recrystallization of the enantiomeric mixtures was suitable for the preparation of enantiopure P-stereogenic organophosphorus compounds. 21,44,78,79…”

“…5,6 Enantioselective synthesis is one of the main sources for optically active organophosphorus compounds. [18][19][20][21] Enantioselective synthesis affords enantiomerically enriched or enantiopure compounds. [18][19][20][21] Enantioselective synthesis affords enantiomerically enriched or enantiopure compounds.…”

Preparation of Enantiomerically Enriched P-Stereogenic Dialkyl-Arylphosphine Oxides via Coordination Mediated Optical Resolution

“…Methods developed for the preparation of P-chiral compounds include stereoselective syntheses from racemic or prochiral starting materials using chiral catalysts [14,15] or auxiliaries [16][17][18][19][20][21][22][23][24], stereospecific transformations of secondary phosphine oxides or phosphinates [16,[25][26][27][28], as well as kinetic [29][30][31][32][33], dynamic kinetic [34][35][36][37][38], chromatographic [39,40] or classical resolutions [41][42][43][44][45][46]. Classical resolutions are generally robust, bench-stable processes that can be scaled up.…”