New pathways in the reaction between the 1,2,4-triphosphole P3C2But2CH(SiMe3)2 and selenium: Crystal and molecular structures of three new cage compounds, P3Se4C2But2CH(SiMe3)2, P3Se3C2But2 H2CH(SiMe3)2 and P5Se2C4But4(CHSiMe3But)

Bilgiç, Sevim; Büyükkıdan, Nurgün; Büyükkıdan, Bülent; Hitchcock, Peter B.; Nixon, John F.

doi:10.1016/j.jorganchem.2007.09.031

Cited by 8 publications

(1 citation statement)

References 26 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…P5 is oxidized in both cases, the bond distances P5-S1 for 10a, P5-Se1 for 11a, and P5-Se3 for 12 (Table 5) are consistent with PvX double bonds. 43,44 The two chalcogenide atoms cause only small changes in the P 5 -deltacyclene cage structure. The differences between 10a and 11a are below 2°for the bond angles and 3 pm for the bond distances outside the PvX bond.…”

Section: X-ray Crystallographymentioning

confidence: 99%

Optically active P₅-deltacyclenes: selective oxidation, ligand properties, and a diastereoselective rearrangement reaction

et al. 2016

View full text Add to dashboard Cite

a Cage-chiral tetra-tert-butyl-P 5 -deltacyclene 5 is accessible as a pair of highly enriched enantiomers 5'and 5''. The only secondary phosphorus atom P1 of the cage can be selectively oxidized by reaction with t-BuOOH. The P1-oxo species 9a' and 9a'', allow the direct determination of their ee values. Oxidation occurs with the complete retention of the optical activity of the compounds. The chiroptical properties of 9a' and 9a'' are strongly dominated by their cage chirality, the oxygen atom does not contribute significantly. Elemental sulfur and selenium oxidize P5 with high preference to yield P5-thio-and P5-seleno-P 5 -deltacyclenes 10 and 11 of the intact cages again. Longer reaction time and more than stoichiometric amounts of selenium, leads to tri-seleno-P 5 -tetracycloundecane 12, a partially opened oxidized rearrangement product. The ligand properties of racemic 9a were determined. Diphosphetane phosphorus atom P2 of 9a is the active donor center to bind a Cr(CO) 5 fragment, but a tautomerization of 9a takes place if [(benzene)RuCl 2 ] 2 is added. A hydrogen atom migrates from P1 to the oxygen atom to form a phosphinous acid ligand. The lone pair of P1 is regenerated and acts as the active ligand function of the cage in this case. As for 5, the base n-BuLi induces an efficient cage rearrangement reaction of 9a, where P1 and the neighboring carbon atom C4 containing its t-Bu substituent change places. C4 moves to its new position without breaking the bond with P5, this way forming the novel P1-oxo-P 5 -norsnoutene cage in a highly diastereoselective process.

show abstract

Section: X-ray Crystallographymentioning

confidence: 99%

Optically active P₅-deltacyclenes: selective oxidation, ligand properties, and a diastereoselective rearrangement reaction

et al. 2016

View full text Add to dashboard Cite

show abstract

Organic Compounds Containing Bonds between Se or Te with P, As, Sb and Bi

Murai

2014

Patai's Chemistry of Functional Groups

View full text Add to dashboard Cite

This chapter describes syntheses, structures, and reactions of the compounds with phosphorus‐selenium double bonds and with at least one carbon‐phosphorus single bond and of their heavier congeners. Among them, phosphane selenides have been the most deeply studied and used as Lewis base catalysts, metal ligands, molecular sensors, and stating materials leading to selenium‐containing nanoparticles. The coupling constants between the phosphorus and selenium atoms are informative on the basicity of the phosphanes. Phosphinoselenoic acid chlorides and secondary phosphanes are frequently used precursors to give a range of phosphinoselenoic acid derivatives, whereas selenation of dichlorophosphanes leads to phosphonoselenoic acid dichlorides, which are converted to a variety of acid derivatives. The selenation of phosphinites also gives phosphinoselenoic acid O ‐esters. Stereochemical course of the substitution reaction at P ‐chiral phosphorus center in the substitution reaction has been elucidated. Some reactions of dimers of diselenoxophosphanes such as Woollin's reagent are also shown. The chapter finally describes examples of phosphane tellurides, arsenic, antimony, and bismuth isologues of phosphane selenides, although these are fewer.

show abstract

Cage Chirality of PC Cage Compounds: Highly Diastereoselective Formation of Diastereomeric P₅‐Deltacyclenes, Separation of Diastereomers, and Removal of the Chiral Auxiliary

Hofmann

Höhn

Heinemann

et al. 2009

Chemistry A European J

View full text Add to dashboard Cite

An effective cyclic addition reaction of diastereomeric (R*)diphenyltin-3,5-di(tert-butyl)-1,2,4-triphosphole derivatives 6 a-c (R* = (-)-cis-myrtanyl (a), (-)-trans-myrtanyl (b), m-(2-bornyl-2-ene)phenyl (c) with two equivalents of tert-butylphosphaalkyne 1 leads to 1:1 mixtures of diastereomeric stannylated pentaphosphadeltacyclene derivatives 7 a-c with seven stereogenic centers in the cage unit. The (-)-cis-myrtanyl derivative 7 a could be separated into its diastereomers; destannylation of diastereomer 7 a(RR) led to the P-H cage 8 as a pure enantiomer. Circular dichroism (CD) spectroscopy of the pure diastereomer 7 a(RR) and the enantiomer 8 give evidence for identical stereoisomers of the P(5)-deltacyclene cage units and prove a strong dominance of the chiral cages over the chiral auxiliary groups with respect to their chiroptical properties. Absolute X-ray structure investigations of the majority of the compounds presented in the paper reveal the details of the stereochemistry of the asymmetric P-C cage units. In this paper we demonstrated for the first time a general preparative route to stereochemically fully defined asymmetric P-C cage compounds by separation of diastereomers and replacement of the chiral auxiliary group.

show abstract

New pathways in the reaction between the 1,2,4-triphosphole P3C2But2CH(SiMe3)2 and selenium: Crystal and molecular structures of three new cage compounds, P3Se4C2But2CH(SiMe3)2, P3Se3C2But2 H2CH(SiMe3)2 and P5Se2C4But4(CHSiMe3But)

Cited by 8 publications

References 26 publications

Optically active P₅-deltacyclenes: selective oxidation, ligand properties, and a diastereoselective rearrangement reaction

Optically active P₅-deltacyclenes: selective oxidation, ligand properties, and a diastereoselective rearrangement reaction

Organic Compounds Containing Bonds between Se or Te with P, As, Sb and Bi

Cage Chirality of PC Cage Compounds: Highly Diastereoselective Formation of Diastereomeric P₅‐Deltacyclenes, Separation of Diastereomers, and Removal of the Chiral Auxiliary

Contact Info

Product

Resources

About

New pathways in the reaction between the 1,2,4-triphosphole P3C2But2CH(SiMe3)2 and selenium: Crystal and molecular structures of three new cage compounds, P3Se4C2But2CH(SiMe3)2, P3Se3C2But2 H2CH(SiMe3)2 and P5Se2C4But4(CHSiMe3But)

Cited by 8 publications

References 26 publications

Optically active P5-deltacyclenes: selective oxidation, ligand properties, and a diastereoselective rearrangement reaction

Optically active P5-deltacyclenes: selective oxidation, ligand properties, and a diastereoselective rearrangement reaction

Organic Compounds Containing Bonds between Se or Te with P, As, Sb and Bi

Cage Chirality of PC Cage Compounds: Highly Diastereoselective Formation of Diastereomeric P5‐Deltacyclenes, Separation of Diastereomers, and Removal of the Chiral Auxiliary

Contact Info

Product

Resources

About

Optically active P₅-deltacyclenes: selective oxidation, ligand properties, and a diastereoselective rearrangement reaction

Optically active P₅-deltacyclenes: selective oxidation, ligand properties, and a diastereoselective rearrangement reaction

Cage Chirality of PC Cage Compounds: Highly Diastereoselective Formation of Diastereomeric P₅‐Deltacyclenes, Separation of Diastereomers, and Removal of the Chiral Auxiliary