Conformational Analysis of 6-Methyl-2-oxo-2-alkoxy-1,2-oxaphosphorinanes.

Bergesen, Knut; Hagberg, Carolina E.; Henriksen, Lars; Holme, Dagny; Lamvik, Aud; Sunde, Erling; Sørensen, Nils Andreas

doi:10.3891/acta.chem.scand.24-2019

Cited by 8 publications

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“…[6]) is in complete agreement with previous results for ribonucleotides (17,(33)(34)(35)(37)(38)(39)(40). In the same way, the correlation for compounds 1 and 3 (eq.…”

supporting

confidence: 91%

“…The 'H nmr spectra were run at 360 MHz on a Bruker WH 360, at 250 MHz on a Cameca, or at 90 MHz on a Perkin-Elmer R32 instrument; '?C nmr spectra were recorded at 25.2 MHz on a Varian XL 100 and "P nmr spectra at 40.5 MHz on a Bruker instrument. All chemical shifts (6) For personal use only.…”

Section: Methodsmentioning

confidence: 99%

“…Furthermore, since the phosphoryl P=O and C3-C2 bonds are cis in compounds 1, 3, and 4, the difference between the relationships (eqs. [5] and [6]) again cannot be attributed to stereochemical factors on phosphorus. However, two differences between 1 (3) and 4 have to be emphasized.…”

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confidence: 98%

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Synthesis and conformational studies of phosphate esters of 1,2-O-isopropylidene-α-D-ribo- and xylo- pentofuranoses

Neeser¹,

Tronchet²,

Charollais³

1983

Can. J. Chem.

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. J . Chem. 61, 1387 (1983).The synthcsis and properties. particularly ' H , "P, and ' " nmr, of new phosphate estcrs of I ,2-0-isopropylidene-a-D-riboand xylo-furanoses arc described. For the cyclic phosphates the configuration at the asymmetric phosphorus atom is determined and for all derivatives the preferred conformation of the furanosc and dioxaphosphorinanc rings and the conformation around the phosphoester bonds are prcscnted. Thc dependency of 'Jr>occ coupling constants on factors other than dihcdral angles is reportcd and discussed.JEAN-RICHARD NEESER, JEAN M . J . TRONCHET ct ETIENNE J . CHAROLLAIS. Can. J . Chem. 61, 1387 (1983). Nous dCcrivons la synthhsc ct les proprietes spectroscopiques (en particulier de rmn ' H , "P ct "C) de nouveaux esters phosphoriques de 0-isopropylidkne-1 ,2-u-D-ribo-et xylo-furannoses. Pour les dCrivCs phosphatc cyclique, la configuration au nivcau de I'atome dc phosphore asyrnetriquc a CtC attribuCe, et pour tous nos composCs, la conformation prCfCrenticlle des cycles furannosique et dioxaphosphorinanne, ainsi que la conformation autour des liaisons phosphoester, sont dCterminCcs. Nous observons Cgalcment une variation des constantes dc couplage Ilr,occ en fonction d'autres facteurs quc les angles dikdres et discutons de la signification de tcls resultats.Considering the importance of pentose phosphates, either by themselves, as structural units of nucleotides, or in metabolic biochemical systems, we were prompted to study derivatives of two important naturally occurring pentoses, namely D-xylose and D-ribose. The observations made on these model compounds might prove useful in the understanding of the conformational properties of biologically important nucleotide derivatives.Syntheses of derivatives 1 to 12 were carried out from 1 ,2-0-isopropylidene-a-D-xylofuranose (A) or 1,2-0-isopropylidene-a-D-ribofuranose (B), as depicted in Fig. 1.Results and discussion 1. Itflared ntzd n~icle~zr magnetic resotzntzce spectroscopy.Conji:guratiot~al assigr~met~t of asjltntnetrical phosphorus atoms in compounds 1 to 4 As previously reported (6-9), the values of the P=O stretching frequency (around 1300 cm-') can be used successfully to assign the configuration of phosphorus atoms of a pair of asymmetrical phosphorus-containing epimeric dioxaphosphorinane rings. Such an assignment is dependent on the orientation of the P=O bond, resulting from the conformation of the heterocycles. For example, in compound 1: v P=O (equatorial) = 1295 cm-', and in compound 2: v P=O (axial) = 1285 cm-'.Tables 1-4 summarize the nrnr data for compounds 1 to 12. As previously reported (7-9), "P chemical shifts of derivatives 1 and 2 show a dependence similar to that of v P=O, as a function of the orientation of the phosphoryl bond: in compound 1, 6 "P = + 16.80 ( P = 0 equatorial) and in compound 2, 6 "P = + 14.10 (P=O axial). Configurational assignment of the phosphorus atom for 3 was deduced from a comparison of the 'H and "C nrnr spectra of 1 and 3. The phosphorus atom configuration for 4 was establish...

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“…[6]) is in complete agreement with previous results for ribonucleotides (17,(33)(34)(35)(37)(38)(39)(40). In the same way, the correlation for compounds 1 and 3 (eq.…”

supporting

confidence: 91%

Section: Methodsmentioning

confidence: 99%

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Synthesis and conformational studies of phosphate esters of 1,2-O-isopropylidene-α-D-ribo- and xylo- pentofuranoses

Neeser¹,

Tronchet²,

Charollais³

1983

Can. J. Chem.

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“…listed in Tables 5 and 6) other than 1,3,2-dioxaphosphorinanes The first compound, 206, will be discussed in Part II, the remainder will be discussed by Y, Z type indicated in the Tables, 2-R-2-OXO-1,2-oxaphosphorinanes (XXV)The 2-substituent-2-oxo-l,2-oxaphosphorinanes 207a,b(119) 208a,b(119,120), 209a,b(119,121), 210a,b(119)(120)(121), Zlla^b(122), and 212a,b(123) all exist as isomer pairs. The general method of synthesis is reaction of dihalide (usually dibromide) with trimethylphosphite to produce the isomeric mixture from which isomers can usually be separated by gas chromatography(119)(120)(121)(122)(123). From infrared stretching frequencies the geometries of the C5 methyl groups of 207a,b and 208a,b were postulated Other Phosphorinane Compounds R(0)P XXV to be solely equatorial for a isomers and at least sometimes axial for b isomers.…”

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confidence: 99%

Structural studies of phosphorinanes

Mosbo

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PART II. THE X-RAY CRYSTAL STRUCTURE OF CYCLOPHOSPHAMIDE 176 6. Keto-enol equilibria of isomeric hydrogen phosphonates 176a and b 7. Enol-intermediate isomerization mechanism of hydrogen phosphonates 176a and b 8. Keto-intermediate isomerization mechanism of hydrogen phosphonates 176a and b vii Page 9. Mechanism of hydrolysis of hydrogen phosphonate 176b to form phosphorous acid and meso-diol 154 10. Mechanism for formation of acetone insertion product of hydrogen phosphonate 176b 156 11. Computer drawing of cyclophosphamide excluding hydrogen atoms 187 12. Drawing of cyclophosphamide including hydrogen atoms 189 13. Computer drawing of the hydrogen bonding of the water of hydration to cyclophosphamide. The chloromethyl groups of the bis-(3-chloroethyl) groups and the hydrogen atoms of cyclophosphamide not involved in hydrogen bonding have been omitted for clarity 194 14. Computer drawing of unit cell of cyclophosphamide including two water molecules. Hydrogen atoms are omitted 197 PART I. SOLUTION STUDIES

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