1987 Fiscal Year Final Research Report Summary
A Facile Preparation of Optically Active Organophosphorus Compounds Using Arbuzov Reaction of Five-membered Ring Phosphorus Compounds
| Project/Area Number |
61550631
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| Research Category |
Grant-in-Aid for General Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Research Field |
Synthetic chemistry
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| Research Institution | Kanazawa University |
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Principal Investigator |
SUGA Sohei Faculty of Technology, Kanazawa University, 工学部, 教授 (40019691)
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| Co-Investigator(Kenkyū-buntansha) |
SEGI Masahito Faculty of Technology, Kanazawa University, 工学部, 助手 (90135046)
NAKAJIMA Tadashi Faculty of Technology, Kanazawa University, 工学部, 教授 (70019735)
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| Project Period (FY) |
1986 – 1987
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| Keywords | Arbuzov Reaction / Optically Active Phosphorus Compound / 環状リン化合物 |
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| Research Abstract |
Optically active organophosphorus compounds have occupied a key position in the stereochemical investigations of nucleophilic substitutions at phosphoryl centers and the study of ligands in transition metal complexes used as asymmetric homogeneous catalysts. A general and practical method for the preparation of these phosphorus compounds has been limited to a few examles. We have investigated a novel synthetic route involving Arbuzov reaction of trivalent cyclic phosphorus compounds, and reported the synthesis of optically active phosphine oxides. In this project, we wish to report a new and convenient method for the preparation of optically active organophosphorus compounds in high enantiomeric purity using Arbuzov reaction of cyclic trivalent 1,3,2-oxazaphospholidine derivatives.
The Arbuzov reaction of trivalent cyclic phosphorus compound, which was synthesized by the reaction of (S)-prolinol with some chlorophosphines RPCl_2 in the presence of trietylamine, with a variety of alkyl halides gave the corresponding pentavalent ringopening compounds with regioselective cleavage of the endo C-O bond as a mixture of diastereomers. After the separation of isomers by column chromatography over silica gel, acid-catalyzed alcoholysis of each diasteremeric isomer resulted in P-N bond cleavage with inversion of configuration at phosphorus atom to afford many kinds of enantiomerically pure organophosphorus compounds. The optical purities of these compounds were measured by a ^1 H-NMR method using a chiral shift reagent.
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