A novel type of nucleoside analogue with penta-coordinated phosphorus

Katalenić, Darinka; Skaric, V.; Klaić, Branimir

doi:10.1016/s0040-4039(00)77021-3

Cited by 10 publications

(6 citation statements)

References 11 publications

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“…It is of interest to configure stable phosphoranes that more closely model proposed enzyme active site transition states than exist at the present time. Efforts to obtain solid-state structural information on pentacoordinate phosphorus containing nucleosides have not been successful despite studies − that have extended over the past 30 or so years. Most of these studies focused on solution NMR measurements and, in many cases, were performed on reaction mixtures without product isolation.…”

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confidence: 99%

Biologically Relevant Phosphoranes: Structural Characterization of a Nucleotidyl Phosphorane

2005

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The first successful crystal structures of biorelevant nucleoside and carbohydrate-based phosphoranes are reported. Employing thymidine, a nucleotidyl phosphorane was synthesized in 90% yield and was shown by X-ray analysis to possess a trigonal bipyramidal geometry. With the use of 1,2-O-isopropylidene-alpha-d-glucofuranose, a carbohydrate-based phosphorane was formed and similarly found to have a trigonal bipyramidal geometry. NMR studies demonstrated the existence of isomerism in solution associated with the nucleotidyl phosphorane and rapid exchange for the carbohydrate-based phosphorane. The geometrical representations reported here are expected to have significant applications associated with active site mechanisms of phosphoryl transfer enzymes, for example, in DNA, RNA, c-AMP, and others.

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confidence: 99%

Biologically Relevant Phosphoranes: Structural Characterization of a Nucleotidyl Phosphorane

2005

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“…3 Only one report appears to be known that proposed a hexacoordinated ribose containing phosphorane (A) based on 31 P NMR data, 4 whereas two reports have mentioned the observation of a cage containing pentacoordinate phosphoranes (B and C), but no structural information was given (Chart 1). 5,6 Herein, we extend our previous work 3 to include bicylic and polycyclic cages containing penta-and hexacoordinated phosphoranes involving the glucofuranose derivatives 1-9 (Chart 2).…”

Section: Introductionmentioning

confidence: 86%

“…31 P NMR (CH 2 Cl 2 ): -59.6. 1 H NMR (CDCl 3 , 295 K): 1.26 (s, 18H, t-Bu), 1.36 (s, 9H, t-Bu), 1.37 (s, 9H, t-Bu), 1.39 (s, 3H, CMe 2 ), 1.52 (s, 3H, CMe 2 ), 3.89 (dd, 3 J POCH ) 22.4, 9.2 Hz, 1H), 3.94 (br, 1H), 4.07 (q, br, 2.0 Hz, 1H), 4.50 (dd, 3 J POCH ) 33.4, 4.0 Hz, 1H), 4.78 (d,2.6 Hz,1H),4.81 (d,3.4 Hz,1H),6.05 (d,3.4 (6). Phosphite 14 (3.10 g, 6.37 mmol) and isopropylideneglucofuranose (1.40 g, 6.36 mmol) were stirred in dichloromethane (110 mL).…”

Section: Methodsmentioning

confidence: 99%

Biologically Relevant Phosphoranes: Synthesis and Structural Characterization of Glucofuranose-Derived Phosphoranes with Penta- and Hexacoordination at Phosphorus

2006

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Carbohydrate-based phosphoranes were synthesized by reacting the appropriate diphenol with phosphorus trichloride followed by the addition of chloralose to form 1 and by the addition of isopropylidene-D-glucofuranose to form 2 and 3. Phosphorane 4 was obtained by reacting 1,2-O-isopropylidene-alpha-D-glucofuranosyl-3,5,6-phosphite (13) with a diphenol. For the synthesis of 5-9, the appropriate phosphite was reacted with isopropylidene-glucofuranose. X-ray analyses of 1-9 were carried out successfully. Hexacoordinated structures resulted via oxygen donor action at phosphorus in the cases of phosphoranes 1-3 and via sulfur donor action for phosphoranes 4-6. Trigonal bipyramidal structures formed for 7-9 with the carbohydrate components occupying axial-equatorial sites. The eight-membered ring of the diphenol moiety with weak or no donor groups in 7-9 occupied diequatorial sites of the trigonal bipyramid. Solution NMR data are in agreement with the assigned solid-state structures. Isomerism between penta- and hexacoordination is present in solution for 7. The isomerism observed for 7 and our previous study showing a rapid exchange process that reorients the carbohydrate component of the trigonal bipyramidal phosphorane suggest that these biophosphoranes may serve as models for active sites of phosphoryl-transfer enzymes. At an active site, this type of pseudorotational behavior provides a mechanism that could bring another active site residue into play and account for a means by which some phosphoryl-transfer enzymes express promiscuous behavior.

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“…Similarly, the regioisomer 5.119 afforded 5.120. 275 The reactions of (PhO) 3 P with azidonucleosides continued to generate interest, which led to the synthesis of compounds 5.121-5.123. 244 Phosphoramidates, which can be obtained with particular ease by condensing azides with silyl phosphites, are of interest as analogues of biologically important phosphates.…”

Section: Addition Of Nucleophilesmentioning

confidence: 99%