Retention of Configuration in the Nucleophilic Substitution Reactions of Some Nine‐Membered Ansa Derivatives of Cyclotriphosphazatriene

Beşli, Serap; Coles, Simon J.; Davies, David B.; Hursthouse, Michael B.; İbişoğlu, Hanife; Kılıç, Adem; Shaw, Robert A.

doi:10.1002/chem.200400311

Cited by 29 publications

(24 citation statements)

References 33 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…It has now been demonstrated crystallographically that inversion of configuration takes place in nucleophilic substitution reactions of macrocyclic phosphazene compounds containing a sixteen-membered ansa ring system, whereas retention of configuration occurs in cyclophosphazenes containing nine-membered ansa rings. [13] We are currently investigating analogous cis-ansa cyclophosphazene compounds with ring sizes intermediate between nine and sixteen to determine at which point or in which range of ring sizes retention changes to inversion. The work will be greatly facilitated by using a marker, such as the spiro-propanoxyamino group, which can be used to distinguish above and below the plane of the cyclophosphazene ring, and hence to investigate retention versus inversion mechanisms.…”

Section: Discussionmentioning

confidence: 99%

“…[13] Previous work has shown that the sixteenmembered ring of the cis-ansa macrocyclic cyclophosphazene derivative 1 is sufficiently large and flexible to take up both cis and trans configurations as a result of nucleophilic substitution reactions, [7,8] and so this same macrocyclic ring was incorporated into compound 3. Reaction of compound 3 with a range of mononucleophiles (2-naphthol, phenol, pyrrolidine and aniline) with different steric demands and different nucleophilicities gave examples of the monosubstituted compound 4 (4a, X = 2-naphthoxy; 4b, X = phenoxy) and of the disubstituted compounds 5a, 5b, 5c and 5d, respectively.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Crystallographic Proof of Double Walden Inversion in Nucleophilic Substitution Reactions of Macrocyclic Cyclotriphosphazene Derivatives

et al. 2005

Self Cite

View full text Add to dashboard Cite

Using X-ray crystallography it is demonstrated unambiguously that a double Walden inversion reaction occurs for successive nucleophilic substitution of the mono-spiropropanoxyamino derivative of the cis-ansa-macrocyclic cyclophosphaz-The spiropropanoxyamino moiety enables groups above and below the plane of the N 3 P 3 ring to be distinguished. The first nucleophilic substitution of compound 3 with X -(e.g., X = 2-naphthoxy) gives N 3 P 3 [O(CH 2 ) 3 4 ]X 2 (5a), in which the macrocyclic ring is cis-ansa again, but it is now on the opposite side of the N 3 P 3 ring from that of the starting material 3 as a result of the second inversion re-

show abstract

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Crystallographic Proof of Double Walden Inversion in Nucleophilic Substitution Reactions of Macrocyclic Cyclotriphosphazene Derivatives

et al. 2005

Self Cite

View full text Add to dashboard Cite

show abstract

“…It is not possible meso form for Type II(4), Type II(5), Type II(7) Type II (8) and Type II (9) configurations. Hence all derivatives would be racemates which are shown for Type II(5) cis (55* [64], 56a [93], 56b [82]), Type II(5) trans (57 [76]), Type II(7) cis (58 [50]). …”

Section: Five Substituted (X Y a B C)mentioning

confidence: 98%

Chiral configurations in cyclophosphazene chemistry

Uslu

Yeşilot

2015

Coordination Chemistry Reviews

View full text Add to dashboard Cite

“…The case of the reaction of compound (9) with the silylated derivative of (2) provides another subtle change in the nature of the nucleophile, further complicated by this reaction being largely driven by the strengths of the Si-F being formed [17 and refs therein]. Much remains to be explained, such as the observation that the mono-ansa compound (4) reacts with pyrrolidine with retention of configuration [45].…”

Section: This Raises the Further Question To What Extent The Spiro Momentioning

confidence: 99%

Competitive formation of spiro and ansa derivatives in the reactions of tetrafluorobutane-1,4-diol with hexachlorocyclotriphosphazene: A comparison with butane-1,4-diol

et al. 2006

Self Cite

View full text Add to dashboard Cite

Beşli, Serap; Coles, Simon J.; Davies, David B.; Eaton, Robert J.; Kılıç, Adem; Shaw, Robert A. (2006) Competitive formation of spiro and ansa derivatives in the reactions of tetrafluorobutane-1,4-diol with hexachlorocyclotriphosphazene: a comparison with butane-1,4-diol. Polyhedron 25 (4): [963][964][965][966][967][968][969][970][971][972][973][974] This is an author-produced version of a paper published in Polyhedron . This version has been peer-reviewed, but does not include the final publisher proof corrections, published layout, or pagination. All articles available through Birkbeck ePrints are protected by intellectual property law, including copyright law. Any use made of the contents should comply with the relevant law. AbstractReaction of hexachlorocyclotriphosphazene, N 3 P 3 Cl 6 (1), in two stoichiometries (1:1.2 and 1:3)with the sodium derivative of the fluorinated diol, 2,2,3,3-tetrafluorobutane-1,4-diol, (2), in THF solution at room temperature afforded six products, whose structures have been characterized by X-ray crystallography and 1 H, 19 F and 31 P NMR spectroscopy: the mono-spiro compound, N 3 P 3 Cl 4 (OCH 2 CF 2 CF 2 CH 2 O), (3), its ansa isomer, (4), a di-spiro derivative N 3 P 3 Cl 2 (OCH 2 CF 2 CF 2 CH 2 O) 2 , (5), its spiro-ansa (6) and non-gem cis bis-ansa (7) isomers and a tri-spiro compound N 3 P 3 (OCH 2 CF 2 CF 2 CH 2 O) 3 , (8). The tri-spiro derivative (8) was also formed in the reaction of the ansa compound (4) with diol (2) in a 1:3 ratio in THF at room temperature.The reactions of (1) with step-wise additions of (2) were also investigated at low temperature (-78 0 C) to give the same range of products as at room temperature. The results of all reactions are compared with previous work on the reactions of (1) with butane-1,4-diol/pyridine mixtures and with the reaction of hexafluorocyclotriphosphazene, N 3 P 3 F 6 (9), with the silyl derivative of the diol (2), (Me 3 SiOCH 2 CF 2 ) 2 , in a 1:0.4 mole ratio in the same solvent, THF.3

show abstract

Retention of Configuration in the Nucleophilic Substitution Reactions of Some Nine‐Membered Ansa Derivatives of Cyclotriphosphazatriene

Abstract: X-ray crystallographic evidence shows that nucleophilic substitution reactions of two different types of cyclophosphazene derivatives with relatively rigid nine-membered ansa rings leads to the first demonstration of retention of configuration in these molecular systems.

Cited by 29 publications

References 33 publications

Crystallographic Proof of Double Walden Inversion in Nucleophilic Substitution Reactions of Macrocyclic Cyclotriphosphazene Derivatives

Crystallographic Proof of Double Walden Inversion in Nucleophilic Substitution Reactions of Macrocyclic Cyclotriphosphazene Derivatives

Chiral configurations in cyclophosphazene chemistry

Competitive formation of spiro and ansa derivatives in the reactions of tetrafluorobutane-1,4-diol with hexachlorocyclotriphosphazene: A comparison with butane-1,4-diol

Contact Info

Product

Resources

About