Solution conformational analysis, crystal structure determination, and anticancer activity of ring-constrained 1,3,2-dioxa- and oxazaphosphorinane cyclophosphamide analogues

Yang, Jianfu; Shah, Dinesh O.; Rao, N. U. M.; Freeman, Wade A.; Soenovsky, George; Gorenstein, David G.

doi:10.1016/s0040-4020(01)89818-5

Cited by 29 publications

(14 citation statements)

References 34 publications

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“…[12,21] Consistent with this, the heteroring conformation of the epimer 20a can be readily verified as a chair from the J-coupling-constant criteria similar to those used above. As in the a series of P-phenyl-substituted compounds, its N3 hydrogen atom is predominantly equatorial ( 2 J 4-Hax,4-Heq = -11.4 Hz).…”

Section: Trans-fused Compounds With Z = N(ch 2 Ch 2 Cl) 2 (20ab)mentioning

confidence: 57%

Synthesis and Conformational Analysis of Saturated cis‐and trans‐1,3,2‐Benzodiazaphosphinine 2‐Oxides

et al. 2006

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By cyclization of N-unsubstituted, and N 1 -or N 3 -methyl-substituted cis-and trans-2-(aminomethyl)cyclohexylamines with phenylphosphonic dichloride, phenyl dichlorophosphate and bis(2-chloroethyl)phosphoramidic dichloride, P epimeric diastereomers a and b of the corresponding 1,3-unsubstituted and 1-or 3-methyl-substituted 2-phenyl-, 2-phenoxy-and 2-[bis(2-chloroethyl)amino]decahydro-1,3,2-benzodiazaphosphinine 2-oxides have been synthesized. The stereochemistry and conformations of the prepared saturated 1,3,2-benzodiazaphosphinine 2-oxides were determined by 1 H, 13 C and 31 P NMR spectroscopy aided by DFT geometry optimizations and J-coupling-constant calculations for selected structures. The 2-phenoxy-substituted trans-

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Section: Trans-fused Compounds With Z = N(ch 2 Ch 2 Cl) 2 (20ab)mentioning

confidence: 57%

Synthesis and Conformational Analysis of Saturated cis‐and trans‐1,3,2‐Benzodiazaphosphinine 2‐Oxides

et al. 2006

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“…Remarkably, all of the reported compounds adopt the double-chair conformation in the crystal, even the P(3)-equatorially substituted congeners 18 ). This can be explained by the fact that the Fig.…”

Section: Conformations In the Solidmentioning

confidence: 93%

3-Fluoro-2,4-dioxa-7-aza-3-phosphadecalin 3-Oxides as Rigid Acetylcholine Mimetics: Conformational Analysis and Direct Evidence of the Anomeric Effect

Furegati

Binder

Linden

et al. 2006

HCA

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Conformational analyses of the P(3)-axially and P(3)-equatorially F-substituted (AE)-cis-and (AE)-trans-2, 4-dioxa-7-aza-3-phosphadecalin 3-oxides (3-fluoro-2,4-dioxa-7-aza-3-phosphabicyclo[4.4.0]decane 3-oxides) were performed. The results are based on independent studies in both solution and the solid state by 1 H-and 31 P-NMR experiments and computational and X-ray crystallographic data. As expected, the axial epimers adopt neat double-chair conformations in solution and in the crystal. Due to the anomeric effect of the electron withdrawing F-substituent, the 2,4-dioxa-3-phospha moiety in the equatorial epimers adopts a mixture of conformations in solution, mainly chair and twist-boat; whereas a neat twist-boat (trans-isomer) and the unusual envelope conformation (cis-isomer) were detected in the solid state. This is the first report of a straight visualization of these conformations and the impact of the anomeric effect in such systems.

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“…[98] [n] Ref. [87] [o] Mean unsigned deviation between the calculated and experimentally measured values.…”

Section: Methods Validationmentioning

confidence: 99%

Conformational Analysis of Saturated trans‐Fused 1,3,2‐Benzoxazaphosphinine 2‐Oxides − DFT Calculation of NMR J(P,H) Coupling Constants

et al. 2004

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The3 J P,H and 4 J P,H spin-spin coupling constants of a selected test set of organophosphorus compounds, calculated by density functional theory (DFT) methods, were found to correlate well with the experimentally measured coupling constants. The contribution of the spin-dipole (SD) term to the coupling constants was found to be negligible, and the diamagnetic and paramagnetic spin-orbit (DSO and PSO) terms cancelled each other, as in the case of J H,H . Calculation solely of the Fermi contact (FC) term was found to be sufficient to provide good estimates of the coupling constants. In the second part of the work, the conformational equilibria and coupling con-

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Solution conformational analysis, crystal structure determination, and anticancer activity of ring-constrained 1,3,2-dioxa- and oxazaphosphorinane cyclophosphamide analogues

Cited by 29 publications

References 34 publications

Synthesis and Conformational Analysis of Saturated cis‐and trans‐1,3,2‐Benzodiazaphosphinine 2‐Oxides

Synthesis and Conformational Analysis of Saturated cis‐and trans‐1,3,2‐Benzodiazaphosphinine 2‐Oxides

3-Fluoro-2,4-dioxa-7-aza-3-phosphadecalin 3-Oxides as Rigid Acetylcholine Mimetics: Conformational Analysis and Direct Evidence of the Anomeric Effect

Conformational Analysis of Saturated trans‐Fused 1,3,2‐Benzoxazaphosphinine 2‐Oxides − DFT Calculation of NMR J(P,H) Coupling Constants

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