An Alternative Advantageous Protocol for Efficient Synthesis of Phosphorothioate Oligonucleotides Utilizing Phenylacetyl Disulfide (PADS)

REFERENCES AND NOTES

• Beaucage , S.L. and Iyer , R.P. 1992 . Advances in the synthesis of oligonucleotides by the phosphoramidite Approach . Tetrahedron , 48 : 2223 – 2311 .
   Web of Science ®Google Scholar
• Beaucage , S.L. and Iyer , R.P. 1993 . Phosphoramidite derivatives and their synthetic applications . Tetrahedron , 49 : 1925 – 1963 .
   Web of Science ®Google Scholar
• Beaucage , S.L. 1999 . “ Oligonucleotide Synthesis. In ” . In Comprehensive Natural Product Chemistry , Edited by: Barton , D.H.R. and Nakanishi , K. vol. 7.05 , 105 New York : Pergamon Press .
   Google Scholar
• Ravikumar , V.T. , Kumar , R.K. , Capaldi , D.C. , Turney , B. , Rentel , C. and Cole , D.L. 2003 . Antisense phosphorothioate oligodeoxyribonucleotide targeted against ICAM-1: Use of I-linker to eliminate 3′-terminal phosphorothioate monoester formation . Org. Proc. Res. Dev. , 7 : 259 – 266 . and references cited therein;
   Web of Science ®Google Scholar
• Krotz , A.H. , McElroy , B. , Scozzari , A.N. , Cole , D.L and Ravikumar , V.T. 2003 . Controlled detritylation of antisense oligonucleotides . Org. Proc. Res. Dev , 7 : 47 – 52 .
   Web of Science ®Google Scholar
• Zhang , Z. and Tang , J-Y. 1998 . Recent development in scale up of modified oligodeoxynucleotides . Current Op. Drug Disc. Develop , 1 : 304 – 313 . and references cited therein
   PubMedGoogle Scholar
• Lima , W.F. , Wu , H. , Nichols , J.G. , Prakash , T.P. , Ravikumar , V. and Crooke , S.T. 2003 . Human RNase H1 uses one tryptophan and two lysines to position the enzyme at the 3′-DNA/5′-RNA terminus of the heteroduplex substrate . J. Biol. Chem. , 278 : 49860 – 49867 .
   PubMed Web of Science ®Google Scholar
• Agrawal , S. and Iyer , R.P. 1997 . Perspectives in antisense therapeutics . Pharmacol. Ther. , 76 : 151 – 160 .
   PubMed Web of Science ®Google Scholar
• Dias , N. and Stein , C.A. 2002 . Antisense oligonucleotides: Basic concepts and mechanisms. . Mol. Cancer Ther. , 1 : 347 – 355 .
   PubMed Web of Science ®Google Scholar
• Bennett , C.F. 2002 . Efficiency of antisense oligonucleotide drug discovery . Antisense Nucleic Acid Drug Dev , 12 : 215 – 224 .
   PubMedGoogle Scholar
• Altmann , K.-H. , Dean , N.M. , Fabbro , D. , Freier , S.M. , Geiger , T. , Haner , R. , Husken , D. , Martin , P. , Monia , B.P. , Muller , M. , Natt , F. , Nicklin , P. , Phillips , J. , Pieles , U. , Sasmor , H. and Moser , H.E . 1996 . Second generation of antisense oligonucleotides: From nuclease resistance to biological efficacy in animals . Chimia , 50 : 168 – 176 .
   Web of Science ®Google Scholar
• “ A number of second-generation phosphorothioate oligonucleotides are in various stages of pre-clinical and clinical trials against APOB-100, PTP-1B, VLA4, TRPM2, survivin, STAT-3. eIF-4E, etc.for the treatment of a variety of diseases such as cancer, psoriasis, diabetes, asthma ” . arthritis, multiple sclerosis, etc.
   Google Scholar
• Suska , A. , Grajkowski , A. , Wilk , A. , Uznanski , B. , Blaszczyk , J. , Wieczorek , M. and Stec , W.J. 1993 . Antisense oligonucleotides: Stereocontrolled synthesis of phosphorothioate oligonucleotides . Pure & Appl. Chem. , 4 : 707 – 714 . and references cited therein;
   Google Scholar
• Stec , W.J. and Wilk , A. 1994 . Stereocontrolled synthesis of oligo(nucleoside phosphorothioate)s . Angew. Chem. Int. Ed. Engl. , 33 : 722 – 709 . and references cited therein
   Web of Science ®Google Scholar
• Lesnikowski , Z.J. 1993 . Stereocontrolled synthesis of P-chiral analogues of oligonucleotides . Bioorg. Chem. , 21 : 127 – 155 .
   Web of Science ®Google Scholar
• Capaldi , D. C. , Gaus , H. J. , Carty , R. L. , Moore , M. N. , Turney , B. J. , Decottignies , S.D. , MaArdle , J. V. , Scozzari , A. N. , Ravikumar , V. T. and Krotz , A. H. 2004 . Formation of 4,4′-dimethoxytrityl-C-phosphonate oligonucleotides . Bioorg. Med. Chem. Lett. , 14 : 4683 – 4690 .
   PubMed Web of Science ®Google Scholar
• Cheruvallath , Z.S. , Kumar , R.K. , Rentel , C. , Cole , D.L. and Ravikumar , V.T. 2003 . Solid phase synthesis of phosphorothioate oligonucleotides utilizing diethyldithiocarbonate disulfide (DDD) as an efficient sulfur transfer reagent . Nucleosides Nucleotides & Nucleic Acids , 22 : 461 – 468 . and references cited therein
   PubMed Web of Science ®Google Scholar
• Cheruvallath , Z.S. , Carty , R.L. , Moore , M.N. , Capaldi , D.C. , Krotz , A.H. , Wheeler , P.D. , Turney , B.J. , Craig , S.R. , Gaus , H.J. , Scozzari , A.N. , Cole , D.L. and Ravikumar , V.T. 2000 . Synthesis of antisense oligonucleotides: Replacement of 3 H-1,2-benzodithiol-3-one 1,1-dioxide (Beaucage reagent) with phenylacetyl disulfide (PADS) as efficient sulfurization reagent: From bench to bulk manufacture of active pharmaceutical ingredient . Org. Proc. Res. Dev. , 4 : 199 – 204 .
   Web of Science ®Google Scholar
• Krotz , A.H. , Gorman , D. , Mataruse , P. , Foster , C. , Godbout , J.D. , Coffin , C.C. and Scozzari , A.N. 2004 . Phosphorothioate oligonucleotides with low phosphate diester content: Greater than 99.9% sulfurization efficiency with “aged” solutions of phenylacetyl disulfide (PADS) . Org. Proc. Res. Dev. , 8 : 852 – 858 .
   Web of Science ®Google Scholar
• Roelen , H.C. P.F. , Kamer , P. C.J. , van den Eist , H. , van der Marel , G.A. and van Boom , J.H. 1991 . A study on the use of phenylacetyl disulfide in the solid-phase synthesis of oligodeoxynucleoside phosphorothioates . Recl. Trav. Chim. Pays-Bas , 110 : 325 – 331 .
   Google Scholar
• Kamer , P.C.J. , Roelen , H.C.P. F. , van den Eist , H. , van der Marel , G.A. and van Boom , J.H. 1989 . An efficient approach toward the synthesis of phosphorothioate diesters via the Schonberg reaction . Tetrahedron Lett. , 30 : 6757 – 6760 .
   Web of Science ®Google Scholar
• Iyer , R.P. , Egan , W. , Regan , J.B. and Beaucage , S.L. 1990 . 3 H-1,2-Benzodithiole-3-one 1,1-dioxide as an improved sulfuring reagent in the solid phase synthesis of oligodeoxyribonucleoside phosphorothioates . J. Am. Chem. Soc. , 112 : 1253 – 1254 .
   Web of Science ®Google Scholar
• Iyer , R.P. , Phillips , L.R. , Egan , W. , Regan , J.B. and Beaucage , S.L. 1990 . The automated synthesis of sulfur-containing oligodeoxyribonucleotides using 3 H-1,2-benzodithiol-3-one 1,1-dioxide as a sulfur-transfer reagent . J. Org. Chem. , 55 : 4693 – 4699 .
   Web of Science ®Google Scholar
• Capaldi , D.C. , Scozzari , A.N. , Cole , D.L. and Ravikumar , V.T. 1999 . Is it essential to use anhydrous acetonitrile in the manufacture of phosphorothioate oligonucleotides . Org. Process Res. Dev , 3 : 485 – 487 .
   Web of Science ®Google Scholar
• Hayakawa , Y. , Hirata , A. , Sugimoto , J. , Kawai , R. , Sakakura , A. and Kataoka , M. 2001 . Effect of molecular sieves in the liquid-phase synthesis of nucleotide via the phosphoramidite method . Tetrahedron , 57 : 8823 – 8826 .
   Web of Science ®Google Scholar
• Capaldi , D. C. , Gaus , H. , Krotz , A. H. , Arnold , J. , Carty , R. L. , Moore , M. N. , Scozzari , A. N. , Lowery , K. , Cole , D. L. and Ravikumar , V. T. 2003 . Synthesis of high-quality antisense drugs. Addition of acrylonitrile to phosphorothioate oligonucleotides: Adduct characterization and avoidance . Org. Proc. Res. Dev. , 7 : 832 – 838 .
   Web of Science ®Google Scholar