The stereochemistry of the alkaline hydrolysis of phosphetanium salts. Change in configuration at phosphorus on ylide formation

Corfield, J. R.; Shutt, J. R.; Trippett, S.

doi:10.1039/c29690000789

Cited by 16 publications

(6 citation statements)

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“…Since the advent of highperformance chromatographic techniques and development of a range of chiral stationary phases (CSPs) resolution of racemic mixtures by chromatographic methods has become a viable alternative to the existing classical methods of resolutions. 90 Early analytical studies91-93 on chiral phosphine derivatives focused mainly on phosphine oxides and typically required the presence of ir-basic, usually condensed aromatic, substituents in their structures (e.g., [64][65][66][67][68][69][70][71] since interac- well as commercially available chiral columns such as Chiracel, Daicel, Chiralpack, etc. Most recently, a range of vinyl phosphine oxides of diversified functional pattern, either cyclic or acyclic, and of E or Z geometry (e.g., [72][73][74][75][76][77][78][79], have been resolved analytically on DACH-DNB columns.98…”

Section: Introductionmentioning

confidence: 99%

Preparation of Scalemic P-Chiral Phosphines and Their Derivatives

Pietrusiewicz¹,

Zabłocka²

1994

Chem. Rev.

632

276

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Section: Introductionmentioning

confidence: 99%

Preparation of Scalemic P-Chiral Phosphines and Their Derivatives

Pietrusiewicz¹,

Zabłocka²

1994

Chem. Rev.

632

276

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“…This stereochemical outcome of substitution reactions is best rationalized in terms of the addition‐elimination mechanism (A−E) involving formation of a penta‐coordinate intermediate with the four‐membered ring occupying the preferred apical‐equatorial position and its pseudorotation before departure of a leaving group from the apical position. Trippett and his coworkers reported at the end of 1960 many examples of the substitution reactions at phosphorus in phosphetans [6a–d] …”

Section: Nucleophilic Substitution Reactions At Tetracoordinate Phosp...mentioning

confidence: 99%

Nucleophilic Substitution at Phosphorus Centres – Old and Recent Studies and a Final Solution of Mechanistic and Related Stereochemical Problems

Mikołajczyk

2024

Chemistry A European J

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Among many problems of a fundamental value in the heteroatom chemistry the mechanism and stereochemistry of nucleophilic substitution reaction at the phosphorus and other heteroatom centres have attracted a great attention of phosphorus chemists already in the middle of the last century. This review, which does not have a comprehensive character, summarizes the selected original contributions aimed at solution of the mechanism of SN2‐P reaction and its relationship with stereochemistry. The breakthrough in these studies has the Westheimer concept and his rules presented at the beginning of this article. Next, a series of papers is presented where the stereochemistry of substitution at phosphorus was investigated in cyclic five‐, four‐ and six‐membered ring phosphorus compound. The majority of these reactions have been found to occur with retention of the P‐configuration. In the third part of this account, the selected examples of substitution reactions at phosphorus in acyclic compounds are discussed. As the results of all the investigations discussed did not allow to ascribe undoubtedly the mechanism (SN2 or A‐E) to the investigated reactions, in the last part the SN‐P reactions are presented the mechanism of which has been established by combination of the stereochemical and DFT‐studies.

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“…1). [30][31][32][33][34][35] Organophosphorus compounds having neither acidic nor basic functional groups may be resolved via the formation of diastereomeric molecular complexes. O,O′-Dibenzoyl-(2R,3R)tartaric acid was suitable for the preparation of optically active phosphine oxides, [36][37][38][39][40][41][42][43] among which a few P-heterocyclic and P-stereogenic examples can be found, such as 1-phenyl-2-phospholene oxide, 11 DuanPhos oxide 44 and a bis-benzophosphetane oxide (Fig.…”

Section: György Keglevichmentioning

confidence: 99%

Resolution of P-stereogenic P-heterocycles via the formation of diastereomeric molecular and coordination complexes (a review)

Bagi

Ujj²,

Czugler

et al. 2016

Dalton Trans.

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TADDOL derivatives and the Ca(2+)-salts of tartaric acid derivatives were found to be versatile and generally applicable resolving agents for the preparation of the enantiomers of P-stereogenic heterocyclic phosphine oxides and phosphinates via the formation of the corresponding diastereomeric molecular and coordination complexes. A few of the diastereomeric intermediates were characterized by single crystal X-ray crystallography to gain insights into the binding mode of the corresponding heterocyclic phosphine oxide ("guest") and the resolving agent ("host") and to study the underlying phenomenon of enantiomeric recognition.

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The stereochemistry of the alkaline hydrolysis of phosphetanium salts. Change in configuration at phosphorus on ylide formation

Abstract: Sunznzary Partial inversions of configuration a t phosphorus occur both on ylide formation from, and alkaline hydrolysjs of, the benzylphosphetanium salts (VII) and (IX).

Cited by 16 publications

References 0 publications

Preparation of Scalemic P-Chiral Phosphines and Their Derivatives

Preparation of Scalemic P-Chiral Phosphines and Their Derivatives

Nucleophilic Substitution at Phosphorus Centres – Old and Recent Studies and a Final Solution of Mechanistic and Related Stereochemical Problems

Resolution of P-stereogenic P-heterocycles via the formation of diastereomeric molecular and coordination complexes (a review)

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