Abstract
A series of enantiomerically pure derivatives of 6-(1-hydroxyalkyl)-1,3,5-triaza-7-phosphatricyclo[3.3.1.1]decane 5 were successfully synthesized for the first time. A series of hydrolytic enzymes was applied in a stereoselective acetylation performed under kinetic resolution conditions. Although the secondary alcohols: α-aryl-hydroxymethyl-PTA (phosphines) 5b–d′, PTA-oxides 8b–d′, and PTA-sulfides 9b–d′ were found to be totally unreactive in the presence of all the enzymes and various conditions applied, the primary alcohols, i.e., the hydroxymethyl derivatives PTA oxide 8a and PTA sulfide 9a, were successfully resolved into enantiomers with moderate to good enantioselectivity (up to 95%). The absolute configurations of the products were determined by an X-ray analysis and chemical correlation.
Highlights
Hydroxyalkyl)-1,3,5-triaza-7-phosphatricyclo[3.3.1.1]decane 5 were successfully synthesized for the first time
We reported the synthesis of phosphine oxide precursors of chiral bidentate and tridentate phosphorus catalysts via hydrolytic enzyme-promoted kinetic resolution of racemic P-chiral or desymmetrization of Pprochiral phosphine oxides, which allowed us to obtain the desired products in enantiopure forms (Scheme 2).[8]
We have applied a series of hydrolytic enzymes in a stereoselective acetylation of 1-hydroxyalkyl derivatives of PTA under the kinetic resolution conditions
Summary
Hydroxyalkyl)-1,3,5-triaza-7-phosphatricyclo[3.3.1.1]decane 5 were successfully synthesized for the first time. A more interesting approach seems to be the introduction of a proper substituent at the methylene group adjacent to the phosphorus atom of PTA (“upper rim”) This should result in the formation of chiral PTA analogues with the stereogenic carbon atom located close to the metal coordinating center on phosphorus. Such a functionalization was presented in several papers, of which the most important was the treatment of the reactive synthon PTA-Li 2 with various electrophiles, e.g., with dichlorophenylphosphine,[2] carbon dioxide, aldehydes, ketones, or imines (Scheme 1).[3]. We have decided to develop a methodology which would enable one to produce chiral nonracemic derivatives of PTA, which would serve as chiral, water-soluble ligands or catalysts
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