Stereochemistry of organophosphorus cyclic compounds. 6. Stereochemistry of the reaction between sulfenyl chlorides and trivalent phosphorus compounds

Mikoajczyk, Marian; Krzywanski, J.; Ziemnicka, B.

doi:10.1021/jo00422a002

Cited by 12 publications

(7 citation statements)

References 5 publications

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“…The reaction was carried out in ether at 0 • C and afforded trans-6(Cl) as a pure diastereomer ( 31 P-NMR assay) in 91% yield (Scheme 3). This reaction, as other reactions of P III -compounds with sulfenyl chlorides [19], gave the desired product 6(Cl) in a stereospecific way with retention of configuration at phosphorus via the intermediate quasi-phosphonium chloride (A). Hence, the isomer of 6(Cl) obtained has the same trans-relation between the C4-methyl group and the chlorine atom This reaction, as other reactions of P III -compounds with sulfenyl chlorides [19], gave the desired product 6(Cl) in a stereospecific way with retention of configuration at phosphorus via the intermediate quasi-phosphonium chloride (A).…”

Section: Resultsmentioning

confidence: 65%

“…This reaction, as other reactions of P III -compounds with sulfenyl chlorides [19], gave the desired product 6(Cl) in a stereospecific way with retention of configuration at phosphorus via the intermediate quasi-phosphonium chloride (A). Hence, the isomer of 6(Cl) obtained has the same trans-relation between the C4-methyl group and the chlorine atom This reaction, as other reactions of P III -compounds with sulfenyl chlorides [19], gave the desired product 6(Cl) in a stereospecific way with retention of configuration at phosphorus via the intermediate quasi-phosphonium chloride (A). Hence, the isomer of 6(Cl) obtained has the same trans-relation between the C 4 -methyl group and the chlorine atom as in the starting phosphorochloridite (7).…”

Section: Resultsmentioning

confidence: 65%

“…In Table 1, all of the chemical shifts and coupling constants, derived from the spectrum, are summarized. This reaction, as other reactions of P III -compounds with sulfenyl chlorides [19], gave the desired product 6(Cl) in a stereospecific way with retention of configuration at phosphorus via the intermediate quasi-phosphonium chloride (A). Hence, the isomer of 6(Cl) obtained has the same trans-relation between the C4-methyl group and the chlorine atom as in the starting phosphorochloridite (7).…”

Section: Resultsmentioning

confidence: 65%

“…In the present work, three basic substitution reactions were examined, namely alkaline hydrolysis, methanolysis and aminolysis. The choice of the first two reactions was due to the fact that they produce diastereomeric thioacids 9 [23] and thionophosphates 12 [19], respectively, which were obtained by us in an independent way and the configuration at phosphorus in both diastereomers of 9 and 12 was firmly established. Moreover, the diastereomeric hydrolysis products 9 as well as thiophosphoryl amides 13 formed in the third reaction do not undergo epimerization at phosphorus under the reaction conditions.…”

Section: Stereochemistry Of Nucleophilic Displacement Reactions At Phosphorus In 2-halogeno-4-methyl-132-dioxaphosphorinan-2-thionesmentioning

confidence: 99%

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Nucleophilic Substitution at Tetracoordinate Phosphorus. Stereochemical Course and Mechanisms of Nucleophilic Displacement Reactions at Phosphorus in Diastereomeric cis- and trans-2-Halogeno-4-methyl-1,3,2-dioxaphosphorinan-2-thiones: Experimental and DFT Studies

et al. 2021

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Geometrical cis- and trans- isomers of 2-chloro-, 2-bromo- and 2-fluoro-4-methyl-1,3,2-dioxaphosphorinan-2-thiones were obtained in a diastereoselective way by (a) sulfurization of corresponding cyclic PIII-halogenides, (b) reaction of cyclic phosphorothioic acids with phosphorus pentachloride and (c) halogen–halogen exchange at PIV-halogenide. Their conformation and configuration at the C4-ring carbon and phosphorus stereocentres were studied by NMR (1H, 31P) methods, X-ray analysis and density functional (DFT) calculations. The stereochemistry of displacement reactions (alkaline hydrolysis, methanolysis, aminolysis) at phosphorus and its mechanism were shown to depend on the nature of halogen. Cyclic cis- and trans-isomers of chlorides and bromides react with nucleophiles (HO−, CH3O−, Me2NH) with inversion of configuration at phosphorus. DFT calculations provided evidence that alkaline hydrolysis of cyclic thiophosphoryl chlorides proceeds according to the SN2-P mechanism with a single transition state according to the potential energy surface (PES) observed. The alkaline hydrolysis reaction of cis- and trans-fluorides afforded the same mixture of the corresponding cyclic thiophosphoric acids with the thermodynamically more stable major product. Similar DFT calculations revealed that substitution at phosphorus in fluorides proceeds stepwise according to the A–E mechanism with formation of a pentacoordinate intermediate since a PES with two transition states was observed.

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Section: Resultsmentioning

confidence: 65%

Section: Resultsmentioning

confidence: 65%

Section: Resultsmentioning

confidence: 65%

Section: Stereochemistry Of Nucleophilic Displacement Reactions At Phosphorus In 2-halogeno-4-methyl-132-dioxaphosphorinan-2-thionesmentioning

confidence: 99%

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Nucleophilic Substitution at Tetracoordinate Phosphorus. Stereochemical Course and Mechanisms of Nucleophilic Displacement Reactions at Phosphorus in Diastereomeric cis- and trans-2-Halogeno-4-methyl-1,3,2-dioxaphosphorinan-2-thiones: Experimental and DFT Studies

et al. 2021

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“…48) (49Cis-and trans-2-methoxy-4-methyl-1,3,2-dioxaphosphorinans react with various sulfenyl chlorides stereospecifically with retention of configuration at phosphorus (Equation (50)). The same stereochemical course was observed for the reaction between optically active isopropyl ethylphosphinate and methylsulphenyl chloride, which stereospecifically leads to the O-isopropyl (R)-ethylphosphonothioate (Equation (51)) [63]. Montchamp proposed chiral menthyl Hhydroxymethylene phosphinate as an available P-chiral synthon for the preparation of chiral phosphines.…”

Section: (28)mentioning

confidence: 57%

Asymmetric Electrophilic Reactions in Phosphorus Chemistry

Kolodiazhna

Kolodiazhnyi

2020

Symmetry

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This review is devoted to the theoretic and synthetic aspects of asymmetric electrophilic substitution reactions at the stereogenic phosphorus center. The stereochemistry and mechanisms of electrophilic reactions are discussed—the substitution, addition and addition-elimination of many important reactions. The reactions of bimolecular electrophilic substitution SE2(P) proceed stereospecifically with the retention of absolute configuration at the phosphorus center, in contrast to the reactions of bimolecular nucleophilic substitution SN2(P), proceeding with inversion of absolute configuration. This conclusion was made based on stereochemical analysis of a wide range of trivalent phosphorus reactions with typical electrophiles and investigation of examples of a sizeable number of diverse compounds. The combination of stereospecific electrophilic reactions and stereoselective nucleophilic reactions is useful and promising for the further development of organophosphorus chemistry. The study of phosphoryl group transfer reactions is important for biological and molecular chemistry, as well as in studying mechanisms of chemical processes involving organophosphorus compounds. New versions of asymmetric electrophilic reactions applicable for the synthesis of enantiopure P-chiral secondary and tertiary phosphines are discussed.

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