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The reaction with chloral of 2-[1-(3-chlorophenyl)-2,2,2-trifluoroethoxy]-5,6-benzo-1,3,2-dioxaphosphorinan-4-one containing a chiral fluorinated exocyclic substituent on phosphorus leads to formation of 2-[1-(3-chlorophenyl)-2,2,2-trifluoroethoxy]-3-(trichloromethyl)-6,7-benzo-1,4,2l 5 -dioxaphosphepin-5-one 2-oxide with a high regio-and stereoselectivity. The molecular and supramolecular structure of the isolated diastereomer was established by means of X-ray diffraction.

ContentsI. Introduction 935 II. The influence of fluorine-containing substituents on the properties of the P(III) atom. Photoelectron 935 spectroscopic and electrochemical data III. Synthesis of fluoroalkoxy-derivatives of P(III) 938 IV. Reactions of fluoroalkyl phosphites 948 V. Conclusion 966 Abstract. The review surveys and gives a systematic account of the electronic structures, syntheses, and chemical properties of fluoroalkyl derivatives of trivalent phosphorus (phosphites, thiophosphites, and amidophophites). The methods of preparation and reactivities of fluoroalkyl phosphites are compared with those of unsubstituted phosphites. The bibliography includes 420 references.