Organic compounds -- part of the class 532-570 series – Organic compounds – Carbohydrates or derivatives
Reexamination Certificate
2007-06-05
2007-06-05
Jiang, S. Anna (Department: 1623)
Organic compounds -- part of the class 532-570 series
Organic compounds
Carbohydrates or derivatives
C536S025330, C536S025300
Reexamination Certificate
active
10454841
ABSTRACT:
A process for the synthesis of phosphorothioate oligonucleotides is provided which comprises assembling an oligonucleotide bound to a solid support in the presence of acetonitrile; prior to cleaving the oligonucleotide from the solid support removing the acetonitrile; and cleaving the oligonucleotide from the solid support. The process is particularly suited to the large scale synthesis of nucleotides. The acetonitrile may be removed from the solid support by one or both of drying and by washing with solvents. Preferred washing solvents comprise trialkylamines.
REFERENCES:
patent: 4458066 (1984-07-01), Caruthers et al.
patent: 4500707 (1985-02-01), Caruthers et al.
patent: 4753985 (1988-06-01), Rosevear et al.
patent: 4795700 (1989-01-01), Dervan et al.
patent: 4973679 (1990-11-01), Caruthers et al.
patent: 5026838 (1991-06-01), Nojiri et al.
patent: 5047524 (1991-09-01), Andrus et al.
patent: 5132418 (1992-07-01), Caruthers et al.
patent: RE34069 (1992-09-01), Koster et al.
patent: 5164491 (1992-11-01), Froehler et al.
patent: 5216141 (1993-06-01), Benner
patent: 5362866 (1994-11-01), Arnold, Jr.
patent: 5407795 (1995-04-01), Kolberg et al.
patent: 5510476 (1996-04-01), Ravikumar et al.
patent: 5514789 (1996-05-01), Kempe
patent: 5548076 (1996-08-01), Froehler et al.
patent: 5554746 (1996-09-01), Ravikumar et al.
patent: 5614621 (1997-03-01), Ravikumar et al.
patent: 5705621 (1998-01-01), Ravikumar
patent: 5714597 (1998-02-01), Ravikumar et al.
patent: 6096881 (2000-08-01), Han et al.
patent: 6111086 (2000-08-01), Scaringe
patent: 6465628 (2002-10-01), Ravikumar et al.
patent: 6768005 (2004-07-01), Mellor et al.
patent: 6858715 (2005-02-01), Ravikumar et al.
patent: 7041816 (2006-05-01), Ravikumar et al.
patent: 2006/0036028 (2006-02-01), Moody et al.
patent: 0 323 152 (1963-07-01), None
patent: 0 288 310 (1988-10-01), None
patent: 1 028 124 (2000-08-01), None
patent: 2003/238586 (2003-08-01), None
patent: WO 92/09615 (1992-06-01), None
patent: WO 94/01446 (1994-01-01), None
patent: WO 97/40458 (1997-10-01), None
patent: WO 00/20431 (2000-04-01), None
patent: WO 00/46231 (2000-08-01), None
patent: WO 01/27126 (2001-04-01), None
patent: WO 01/96358 (2001-12-01), None
[R] Ravikumar et al. (VIII), “Efficient Synthesis of Deoxyribonucleotide Phosphorothioates by the Use of DMT Cation Scavenger,” Tetrahedron Letters, 36(37), 6587-6590 (Sep. 11, 1995).
(S) Krotz et al. (I), “Synthesis and Deprotection of β-Silylethyl Protected O, O, O- and O, O, S-Trialkylphosphorothioates,” Tetrahedron Letters, 37(12), 1999-2002 (Mar. 18, 1996).
(T) Krotz et al. (II), “Phosphorothioate Oligonucleotides: Largely Reduced (N-10-Mer and Phosphodiester Content Through the Use of Dimeric Phosphoramidite Synthons,” Bioorganic & Medicinal Chemistry Letters, 7(1), 73-78 (Jan. 7, 1997).
(U) Krotz et al. (III), “Phosphorothioates: β-Fragmentation Versus β-Silicon Effect,” Angewandte Chemie Intl. Ed., 34(21), 2406-2409 (Nov. 17, 1995).
(V) Gait, “An Introduction to Modern Methods of DNA Synthesis,” Ch. 1 in Oligonucleotide Synthesis—A Practical Approach, Gait (ed.), IRL Press, Washington, DC, 1984, only pp. 1-22 and index/title supplied.
(W) Sproat et al. (I), “2'-O-Methyloligoribonucleotides: Synthesis and Applications,” Ch. 3 in Oligonucleotides and Analogues—A Practical Approach, Eckstein (ed.), IRL Press, New York, NY, 1991, only title and text pp. 49-86 supplied, see especially p. 52.
(X) Connolly, “Oligonucleotides Containing Modified Bases,” Ch. 7 in Oligonucleotides and Analogues—A Practical Approach, Eckstein (ed.), IRL Press, New York, NY, 1991, only title and text pp. 155-183 supplied, see especially p. 157.
(Y) Conway et al., “Site-Specific Attachment of Labels to the DNA Backbone,” Ch. 9 in Olignucleotides and Analogues—A Practical Approach, Eckstein (ed.), IRL Press, New York, NY, 1991, only title and text pp. 211-239 supplied, see especially p. 218.
(Z) Atkinson et al., “Solid-Phase Synthesis of Oligonucleotides by the Phosphite Triester Method,” Ch. 3 in Oligonucleotide Synthesis—A Practical Approach, Gait (ed.), IRL Press, Washington, DC, Jul. 1985, only title and text pp. 35-81 supplied, see especially p. 80.
(RA) Sproat et al. (II), “Solid-Phase Synthesis of Oligodeoxynucleotides by the Phosphotriester Method,” Ch. 4 in Oligonucleotide Synthesis—A Practical Approach, Gait (ed.), IRL Press, Washington, DC, Jul. 1985, only title and text pp. 83-115 supplied , see especially p. 111.
(SA) Septak, “Kinetic Studies on Depurination and Detritylation of CPG-Bound Intermediates During Olignucleotide Synthesis,” Nucleic Acids Research, 24(15), 3053-3058 (1996).
(TA) Horn et al. (I), “Solid Support Hydrolysis of Apurinic Sites in Synthetic Oligonucleotides for Rapid and Efficient Purification on Reverse-Phase Cartridges,” Nucleic Acids Research, 16(24), 11559-11571 (Dec. 23, 1988).
(UA) Horn et al. (II), “Chemical Synthesis and Characterization of Branched Oligodeoxyribonucleotides (bDNA) for Use as Signal Amplifiers in Nucleic Acid Quantification Assays,” Nucleic Acids Research, 25(23), 4842-4849 (Dec. 1, 1997).
(VA) Horn et al. (III), “The Synthesis of Branched Oligonucleotides as Signal Amplification Multimers for Use in Nucleic Acid Assays,” Nucleosides and Nucleotides, 8(5&6), 875-877 (Jul./Sep. 1989).
(WA) Horn et al. (IV), “Forks and Combs and DNA: The Synthesis of Branched Oligodeoxyribonucleotides,” Nucleic Acids Research, 17(17), 6959-6967 (Sep. 12, 1989).
(XA) Perrin et al., Purification of Laboratory Chemicals, Pergamon Press, New York, NY, 1966, only pp. 54-55, 74-75, 78-79. 82-93, 96-97. 100-101, 108-113, 118-119, 126-133, 138-141, 158-159, 168-169, 178-179, 184-187, 190-191, 198-199, 202-205, 210-211 and 216-217 supplied.
(YA) Aldrich Catalog/Handbook of Find Chemicals, Aldrich Chemical Company, Milwaukee, WI, 1994-1995, only pp. 1091-1092, 1094, 1096, 1123, 1308, 1313, 1328, 1359-1360, 1371, 1375, 1380, 1384, 1398-1399, 1401, 1403, 1407, 1423, 1461 and 1462 supplied.
(ZA) Greene et al., Protective Groups in Organic Synthesis, Second Edition, John Wiley & Sons, New York, NY, 1991, only pp. 60-65 supplied.
(RB) Xu et al., “Use of 1, 2, 4-Dithiazolidine-3, 5-dione (DtsNH) and 3-Ethoxy-1, 2, 4-Dithiazolidine-5-one (EDITH) for Synthesis of Phosphorothioate-Containing Oligodeoxyribonucleotides,” Nucleic Acids Research, 24(9), 1602-1607 (1996).
(SB) Capaldi et al., “Is IT Essential to USe Anhydrous Acetonitrile in the Manufacture of Phosphorothioate Oligonucleotides?” Organic Process Research & Development, 3(6), 485-487 (1999); WEB published Sep. 1, 1999.
(TB) Oka et al., “An Oxazaphospholidine Approach for the Stereocontrolled Synthesis of Oligonucleoside Phosphorothioates,” Journal of the American Chemical Society, 125(27), 8307-8317 (2003; WEB published on Jun. 14, 2003.
(UB) Krotz et al. (IV), “Phosphorothioate Oligonucleotides with Low Phosphate Diester Content: Greater than 99.9% Sulfurization Efficiency with ‘Aged’ Solutions of Phenylacetyl Disulfide (PADS),” Organic Process Research & Development, 8(6), 852-858 (2004); WEB published on Oct. 20, 2004.
Ravikumar et al. (VIII), “Efficient Synthesis of Deoxyribonucleotide Phosphorothioates by the Use of DMT Cation Scavenger,”Tetrahedron Letters, 36(37), 6587-6590 (Sep. 11, 1995).
Krotz et al. (I), “Synthesis and Deprotection of β-Silylethyl Protected O, O, O- and O, O, S-Trialkylphosphorothioates,”Tetrahedron Letters, 37(12), 1999-2002 (Mar. 18, 1996).
Krotz et al. (II), “Phosphorothioate Oligonucleotides: Largely Reduced (N-10-Mer and Phosphodiester Content Through the Use of Dimeric Phosphoramidite Synthons,”Bioorganic&Medicinal Chemistry Letters, 7(1), 73-78 (Jan. 7, 1997).
Krotz et al. (III), “Phosphorothioates: &#x
Douglas Mark Edward
Mellor Ben James
Wellings Donald Alfred
Avecia Limited
Jiang S. Anna
Pillsbury Winthrop Shaw & Pittman LLP
LandOfFree
Process for the preparation of phosphorothioate... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Process for the preparation of phosphorothioate..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Process for the preparation of phosphorothioate... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-3872610