Abstract
2-Alkoxy-2-thiono-1,3,2-oxathiaphospholanes are readily transformed into phosphorothioate monoesters of the corresponding alcohols in a one-pot process, involving the reaction with 3-hydroxypropionitrile in the presence of DBU, followed by treatment with aqueous ammonia. In this way a series of nucleoside-3′-O - and 5′-O -phosphorothioates were prepared, as well as phosphorothioate derivatives of selected polyols.
Key words
nucleosides - polyols - thiophosphorylation - oxathiaphospholanes - ring-opening condensation
References
1a Eckstein F.
J. Am. Chem. Soc.
1996,
88:
4292
1b Eckstein F.
Tetrahedron Lett.
1967,
1157
1c Eckstein F.
J. Am. Chem. Soc.
1970,
92:
4718
2 Murray AW.
Atkinson MR.
Biochemistry
1968,
7:
4023
3 Tsai M.-D.
Chang T.-T.
J. Am. Chem. Soc.
1980,
102:
5416
4 Eckstein F.
Annu. Rev. Biochem.
1985,
54:
367
5a Sheu K.-F.
Richard JP.
Frey PA.
Biochemistry
1979,
18:
5548
5b Connolly BA.
Romaniuk PJ.
Eckstein F.
Biochemistry
1982,
21:
1983
6a Brody RS.
Frey PA.
Biochemistry
1981,
20:
1245
6b Potter BVL.
Eckstein F.
J. Biol. Chem.
1984,
259:
14243
7 Chen J.-T.
Benkovic SJ.
Nucleic Acids Res.
1983,
11:
3737
8 Chladek S.
Nagyvary J.
J. Am. Chem. Soc.
1972,
94:
2079
9 Cook AF.
J. Am. Chem. Soc.
1970,
92:
190
10a Ma A.
Smrt J.
Coll. Czech. Chem. Commun.
1973,
38:
2953
10b Kresse J.
Nagpal KL.
Nagyvary J.
Uchic JT.
Nucleic Acids Res.
1975,
2:
1
11a Uhlmann E.
Engels J.
Tetrahedron Lett.
1986,
27:
1023
11b Thuong NT.
Chassignol M.
Tetrahedron Lett.
1987,
28:
4157
11c Francois J.-C.
Saison-Behmoaras T.
Barbier C.
Chassignol M.
Thuong NT.
Helene C.
Proc. Natl. Acad. Sci. U.S.A
1989,
86:
9702
12a Horn T.
Urdea MS.
Tetrahedron Lett.
1986,
27:
4705
12b Gryaznov SM.
Letsinger RL.
Nucleic Acids Res.
1993,
21:
1403
12c Xu Y.
Kool ET.
Nucleic Acids Res.
1998,
26:
3159
13 Baker GR.
Billington DC.
Gani D.
Tetrahedron
1991,
47:
3895
14 Alefelder S.
Patel BK.
Eckstein F.
Nucleic Acids Res.
1998,
26:
4983
15 Szczepanik MB.
Desaubry L.
Johnson RA.
Tetrahedron Lett.
1998,
39:
7455
16a Stec WJ.
Grajkowski A.
Kozio M.
UznaÒ B.
Nucleic Acids Res.
1991,
19:
5883
16b Stec WJ.
Grajkowski A.
Karwowski B.
KobylaÒ A.
Kozio M.
Misiura K.
Okruszek A.
Wilk A.
Guga P.
Boczkowska M.
J. Am. Chem. Soc.
1995,
117:
12019
16c
16d Stec WJ.
Karwowski B.
Boczkowska M.
Guga P.
Kozio M.
Sochacki M.
Wieczorek MW.
B J.
J. Am. Chem. Soc.
1998,
120:
7156
17 A linear gradient 0.05→0.5 M triethylammonium bicarbonate (TEAB) was used as eluent.
18 RP HPLC purification of nucleoside 5′-O - or 3′-O -phosphorothioates was performed portionwise, on a semi-preparative ODS-Hypersil column (C18 ), with a linear gradient of 0 → 40% acetonitrile in 0.1 M TEAB as eluent (2%/min). Pure products were collected at retention times ranging from 8.3 to 11.1 min.
19 Kozio M.
Gendaszewska E.
Maszewska M.
Stein CA.
Stec WJ.
Blood
2001,
98:
995
20 DaCosta CP.
Krajewska D.
Okruszek A.
Stec
J W.
Sigel H.
J. Biol. Inorg. Chem.
2002,
7:
405
21 Guga P.
DomaÒ K.
Stec WJ.
Angew. Chem. Int. Ed.
2001,
40:
610
22 Guga, P.; DomaÒski, K.; unpublished results.
23 Baraniak J.
Wasilewska E.
Korczy D.
Stec WJ.
Tetrahedron Lett.
1999,
40:
8603
24a Ushakova IP.
Tuvin MY.
Serebrennikova GA.
Kol’tsova GN.
Vyazova EP.
Rosenberg GY.
Evstigneeva RP.
Bioorg. Khim.
1985,
11:
845
24b Chuvilin AN.
Serebrennikova GA.
Evstigneeva RP.
Kol’tsova GN.
Vyazova EP.
Rosenberg GY.
Bioorg. Khim.
1985,
11:
187
24c Chuvilin AN.
Serebrennikova GA.
Evstigneeva RP.
Bioorg. Khim.
1990,
16:
1157
25 Varnum JM.
Baraniak J.
Stec WJ.
Brenner C.
BMC Chem. Biol.
2001,
1:
1
26 Okruszek A.
Olesiak M.
Krajewska D.
Stec WJ.
J.Org.Chem.
1997,
62:
2269
