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Nucleophilic substitution at phosphorus: stereochemistry and mechanisms |
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| Authors: | Oleg I Kolodiazhnyi Anastasy Kolodiazhna |
| Institution: | Institute of Bioorganic Chemistry and Petrochemistry, National Academy of Sciences of Ukraine, Murmanska Str. 1, Kiev, Ukraine |
| Abstract: | This review is devoted to the stereochemistry of nucleophilic substitution reactions at phosphorus. The study of the reactions of phosphoryl group transfer is important for biological and molecular chemistry. The stereochemistry and mechanisms of SN1(P) monomolecular and SN2(P) bimolecular nucleophilic substitution reactions of organophosphorus compounds are discussed. It has been shown that hydrolysis of many natural phosphates proceeds according to the monomolecular SN1(P) mechanism via the formation of metaphosphate intermediate (PO3?). SN2(P) nucleophilic substitution at chiral trivalent or pentavalent phosphorus compounds proceeds via the formation of penta-coordinated transition state or pentacoordinate intermediate. |
| Keywords: | Ac acetyl An anisyl Ar aryl ATP adenosine triphosphate Bn benzyl Boc Bu butyl Bz benzoyl cat catalyst conv conversion Cy cyclohexyl DABCO 1 4-diazabicyclo[2 2 2]octane DBU 1 8-diazabicyclo[5 4 0]undec-7-ene de diastereomeric excess DMF dmpe 1 2-bis(dimethylphosphino)ethane DMSO dimethylsulfoxide EA elimination–addition ee enantiomeric excess Et ethyl Fmoc 9-fluorenylmethoxycarbonyl Fu furanyl GF1 GF2 Hex hexyl L Lig ligand Me methyl Mes mesyl Mnt MTBE nphth naphthyl Oct octyl Pent pentyl Ph phenyl Piv pivaloyl Pr propyl py pyridyl TADDOL a a a0 a0-tetraaryl-1 3-dioxolane-4 5-dimethanol TBAB TBP bipyramidal intermediate TBS TC transition complex THF tetrahydrofuran Tf trifluoromethanesulfonyl TFA trifluoroacetic acid TMS trimethylsilyl Tl tolyl Ts 4-toluenesulfonyl (tosyl) TS transition state |
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