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21. 发明申请

US20080194502A1 Protecting Groups for RNA Synthesis 有权
标题翻译： RNA合成保护基
公开(公告)号：US20080194502A1
公开(公告)日：2008-08-14
申请号：US11949667
申请日：2007-12-03
申请人： Douglas J. Dellinger , Brian Stell , Marvin H. Caruthers
发明人： Douglas J. Dellinger , Brian Stell , Marvin H. Caruthers
IPC分类号： A61K31/7052 , C07H19/00
CPC分类号： C07H19/00 , Y02P20/55
摘要： Aspects of the invention include 2′ protected nucleoside monomers that are protected at the 2′ site with orthoester-type protecting groups. The 2′ protected monomers also include a second, aryl carbonate-type, protecting group. Aspects of the invention further include nucleic acids that include the protecting groups of the invention, as well as methods of synthesizing nucleic acids using the protecting groups of the invention.
摘要翻译：本发明的方面包括2'保护的核苷单体，其在2'位保护，并具有原酸酯型保护基。 2'保护的单体还包括第二芳基碳酸酯型保护基。本发明的方面还包括包含本发明的保护基团的核酸以及使用本发明的保护基合成核酸的方法。

22. 发明授权

US07101986B2 Methods of synthesizing oligonucleotides using carbonate protecting groups and alpha-effect nucleophile deprotection 有权
公开(公告)号：US07101986B2
公开(公告)日：2006-09-05
申请号：US10648740
申请日：2003-08-25
申请人： Douglas J. Dellinger , Marvin H. Caruthers , Jason R. Betley
发明人： Douglas J. Dellinger , Marvin H. Caruthers , Jason R. Betley
IPC分类号： C07H21/00 , C07H21/02 , C07H21/04 , C12Q1/68
CPC分类号： C07H19/10 , C07B2200/11 , C07H19/20 , C07H21/00 , C07H21/04 , C40B40/06 , C40B50/14 , Y02P20/55
摘要： The invention provides methods for synthesizing oligonucleotides using nucleoside monomers having carbonate protected hydroxyl groups that are deprotected with α-effect nucleophiles. The α-effect nucleophile irreversibly cleave the carbonate protecting groups while simultaneously oxidizing the internucleotide phosphite triester linkage to a phosphodiester linkage. The procedure may be carried out in aqueous solution at neutral to mildly basic pH. The method eliminates the need for separate deprotection and oxidation steps, and, since the use of acid to remove protecting groups is unnecessary, acid-induced depurination is avoided. Fluorescent or other readily detectable carbonate protecting groups can be used, enabling monitoring of individual reaction steps during oligonucleotide synthesis. The invention is particularly useful in the highly parallel, microscale synthesis of oligonucleotides.

23. 发明授权

US6008400A Orthoester reagents for use as protecting groups in oligonucleotide synthesis 失效
标题翻译：用于寡核苷酸合成中的保护基的异戊醇试剂
公开(公告)号：US6008400A
公开(公告)日：1999-12-28
申请号：US994824
申请日：1997-12-19
申请人： Stephen Scaringe , Marvin H. Caruthers
发明人： Stephen Scaringe , Marvin H. Caruthers
IPC分类号： C12Q1/68 , C07H1/00 , C07H19/06 , C07H19/067 , C07H19/073 , C07H19/10 , C07H19/16 , C07H19/167 , C07H19/173 , C07H19/20 , C07H21/00 , C07H21/02 , C07H21/04 , C07C255/11 , C07C43/30 , C07C43/32 , C07C255/49
CPC分类号： C07H19/06 , C07H19/10 , C07H19/16 , C07H19/20 , C07H21/00 , Y02P20/55
摘要： Phosphoramidite oligonucleotide synthesis is facilitated by the use of fluoride-labile 5' silyl protecting groups. RNA synthesis is improved by the use of 2 orthoester protecting groups. Reactions are conducted on a solid phase support and acidic deprotection conditions are avoided, as is the necessity of oxidizing the phosphite linkage between each coupling reaction.
摘要翻译：通过使用氟化物不稳定的5'甲硅烷基保护基促进了亚磷酰胺寡核苷酸合成。通过使用2个原酸酯保护基来提高RNA合成。反应在固相载体上进行，并且避免了酸性脱保护条件，以及在每个偶联反应之间氧化亚磷酸酯键的必要性。

24. 发明授权

US5132418A Process for preparing polynucleotides 失效
标题翻译：制备多核苷酸的方法
公开(公告)号：US5132418A
公开(公告)日：1992-07-21
申请号：US601813
申请日：1984-06-18
申请人： Marvin H. Caruthers , Mark D. Matteucci
发明人： Marvin H. Caruthers , Mark D. Matteucci
IPC分类号： B01J19/00 , C07H19/04 , C07H21/00 , C07H23/00 , C40B40/06 , C40B60/14
CPC分类号： C07H21/00 , B01J19/0046 , C07H19/04 , C07H23/00 , B01J2219/00286 , B01J2219/00389 , B01J2219/005 , B01J2219/0059 , B01J2219/00596 , B01J2219/0068 , B01J2219/00686 , B01J2219/00722 , C40B40/06 , C40B60/14 , Y02P20/582
摘要： This invention is a process for the production of oligonucleotides which comprises:(a) converting an inorganic polymer into a coupling agent-polymer;(b) combining the coupling agent-polymer with a blocked nucleoside to obtain a blocked nucleoside-modified support; and(c) removing the blocking group from the blocked nucleoside-modified support to provide for the coupling of nucleotides to the nucleoside-modified support.
摘要翻译：本发明是制备寡核苷酸的方法，其包括：（a）将无机聚合物转化为偶联剂 - 聚合物; （b）将偶联剂 - 聚合物与封闭的核苷组合以获得封闭的核苷修饰的载体; 和（c）从封闭的核苷修饰的载体中除去封闭基团以提供核苷酸与核苷修饰的载体的偶联。

25. 发明申请

US20120238737A1 THIOCARBON-PROTECTING GROUPS FOR RNA SYNTHESIS 有权
标题翻译：用于RNA合成的THIOCARBON保护组
公开(公告)号：US20120238737A1
公开(公告)日：2012-09-20
申请号：US13485592
申请日：2012-05-31
申请人： Douglas J. Dellinger , Agnieszka Sierzchala , John Turner , Joel Myerson , Zoltan Kupihar , Fernando Ferreira , Marvin H. Caruthers , Geraldine F. Dellinger
发明人： Douglas J. Dellinger , Agnieszka Sierzchala , John Turner , Joel Myerson , Zoltan Kupihar , Fernando Ferreira , Marvin H. Caruthers , Geraldine F. Dellinger
IPC分类号： C07H1/00 , C07H19/20 , C07H21/02 , C07H19/10
CPC分类号： C07H19/073 , C07H13/12 , C07H19/16 , C07H21/02 , Y02P20/55
摘要： Aspects of the invention include 2′ protected nucleoside monomers that are protected at the 2′ site with thiocarbon protecting groups. Thiocarbon protecting groups of interest include thiocarbonate, thionocarbonate, dithiocarbonate groups, as well as thionocarbamate protecting groups. Aspects of the invention further include nucleic acids that include the protecting groups of the invention, as well as methods of synthesizing nucleic acids using the protecting groups of the invention.
摘要翻译：本发明的方面包括2'受保护的核苷单体，其在2'位置被硫代保护基团保护。感兴趣的硫代碳保护基包括硫代碳酸酯，硫代碳酸酯，二硫代碳酸酯基，以及硫羰氨基保护基。本发明的方面还包括包含本发明的保护基团的核酸以及使用本发明的保护基合成核酸的方法。

26. 发明申请

US20090082554A1 Thiocarbonate linkers for polynucleotides 有权
标题翻译：多核苷酸的硫代碳酸酯接头
公开(公告)号：US20090082554A1
公开(公告)日：2009-03-26
申请号：US11903821
申请日：2007-09-24
申请人： Douglas J. Dellinger , Zoltan Timar , Joel Myerson , Geraldine Dellinger , Marvin H. Caruthers
发明人： Douglas J. Dellinger , Zoltan Timar , Joel Myerson , Geraldine Dellinger , Marvin H. Caruthers
IPC分类号： C07H21/00 , C07H21/02 , C07H21/04
CPC分类号： C07H21/00 , C07H21/02 , C07H21/04
摘要： In various embodiments of the invention, novel compositions having a polynucleotide bound to a substrate via a cleavable linker are provided, and methods of cleaving a polynucleotide from a substrate are provided.
摘要翻译：在本发明的各种实施方案中，提供了具有通过可切割连接子与底物结合的多核苷酸的新型组合物，并提供了从底物切割多核苷酸的方法。

27. 发明授权

US07427679B2 Precursors for two-step polynucleotide synthesis 失效
标题翻译：两步多核苷酸合成的前体
公开(公告)号：US07427679B2
公开(公告)日：2008-09-23
申请号：US10652048
申请日：2003-08-30
申请人： Douglas J. Dellinger , Agnieszka B. Sierzchala , Marvin H. Caruthers
发明人： Douglas J. Dellinger , Agnieszka B. Sierzchala , Marvin H. Caruthers
IPC分类号： C07H19/10 , C07H19/20
CPC分类号： C07H21/00 , C07H19/00 , Y02P20/55
摘要： Precursors for use in the synthesis of polynucleotides are disclosed. The precursors include a heterocyclic base having an exocyclic amine group and a substituted or unsubstituted triaryl methyl protecting group bound to the exocyclic amine group. In particular embodiments, the precursor has the structure: wherein: O and H represent oxygen and hydrogen, respectively, R1 is hydrido, hydroxyl, protected hydroxyl, lower alkyl, modified lower alkyl, or alkoxy, one of R2 or R3 is a hydroxyl protecting group; and the other of R2 or R3 is a reactive group capable of reacting with a reactive site hydroxyl, Base is a heterocyclic base having an exocyclic amine group, and Tram is a triaryl methyl group having the structure (V) wherein the broken line represents a bond to the amino nitrogen of the exocyclic amine group, and R4, R5 and R6 are independently selected from unsubstituted or substituted aryl groups, provided that at least one of R4, R5, and R6 is an aryl group other than phenyl and other than substituted phenyl.
摘要翻译：公开了用于合成多核苷酸的前体。前体包括具有环外胺基的杂环碱基和与环外胺基结合的取代或未取代的三芳基甲基保护基。在具体实施方案中，前体具有以下结构：其中：O和H分别表示氧和氢，R 1是氢，羟基，被保护的羟基，低级烷基，经修饰的低级烷基或烷氧基，R 2或R 3之一是羟基保护基; R 2或R 3中的另一个为可与反应性位点羟基反应的反应性基团，碱基为具有环外胺基的杂环碱基，Tram为具有结构（V）的三芳基甲基，其中虚线表示与环外胺基团的氨基氮的键，并且R 4，R 5和R 6独立地选自未取代或取代的芳基，条件是R 4，R 5和R 6中的至少一个是芳基除苯基以外的基团，而不是取代的苯基。

28. 发明申请

US20080206850A1 Methods and compositions for DNA synthesis 审中-公开
标题翻译： DNA合成的方法和组合物
公开(公告)号：US20080206850A1
公开(公告)日：2008-08-28
申请号：US11713221
申请日：2007-02-28
申请人： Douglas J. Dellinger , Geraldine F. Dellinger , Marvin H. Caruthers
发明人： Douglas J. Dellinger , Geraldine F. Dellinger , Marvin H. Caruthers
IPC分类号： C07H21/04 , C12M1/34
CPC分类号： C07H21/04 , Y02P20/55
摘要： In some embodiments, the present disclosure relates to new phosphoramidite compositions, that have Silyl-containing carbonate or thiocarbonate or ether as 5′-hydroxyl protecting groups useful of the synthesis of DNA, and in particular for the synthesis of long sequences of DNA (e.g., >50 mer). In some embodiments, there are provided methods for simultaneous oxidation of the internucleoside phosphate triester linkages and removal of the 5′-hydroxyl-protecting group, making this process a new 2-step DNA synthesis, that involves the use of peroxyanions in combination with fluoride anions.
摘要翻译：在一些实施方案中，本公开涉及新的亚磷酰胺组合物，其具有含有甲硅烷基的碳酸酯或硫代碳酸酯或醚作为可用于合成DNA的5'-羟基保护基团，特别是用于合成长序列DNA（例如，> 50 mer）。在一些实施方案中，提供了同时氧化核苷磷酸三酯键并除去5'-羟基保护基团的方法，使该方法成为新的2-步DNA合成，其涉及使用过氧阴离子与氟化物阴离子

29. 发明申请

US20080146787A1 Thioether substituted aryl carbonate protecting groups 有权
标题翻译：硫醚取代的芳基碳酸酯保护基
公开(公告)号：US20080146787A1
公开(公告)日：2008-06-19
申请号：US11897898
申请日：2007-08-31
申请人： Zoltan Timar , Zoltan Kupihar , Douglas J. Dellinger , Marvin H. Caruthers
发明人： Zoltan Timar , Zoltan Kupihar , Douglas J. Dellinger , Marvin H. Caruthers
IPC分类号： C07H21/00 , C07H19/04 , C07H21/04 , C07H21/02
CPC分类号： C07H19/04 , C07H21/00 , C07H21/02 , C07H21/04 , Y02P20/55
摘要： Embodiments of the invention include thioether substituted aryl carbonate protecting groups, and nucleoside monomers protected with thioether substituted aryl carbonate protecting groups. Aspects of the invention further included methods of synthesizing nucleic acids, e.g., oligonucleotides, using such protected nucleoside monomer monomers, as well as nucleic acids produced using methods of the invention and compositions thereof.
摘要翻译：本发明的实施方案包括硫醚取代的芳基碳酸酯保护基，和用硫醚取代的芳基碳酸酯保护基保护的核苷单体。本发明的方面还包括使用这种受保护的核苷单体/单体合成核酸例如寡核苷酸的方法，以及使用本发明的方法和其组合物制备的核酸。

30. 发明授权

US07271258B2 Methods of synthesizing oligonucleotides using carbonate protecting groups and alpha-effect nucleophile deprotection 有权
标题翻译：使用碳酸酯保护基和α-效应亲核体脱保护合成寡核苷酸的方法
公开(公告)号：US07271258B2
公开(公告)日：2007-09-18
申请号：US11453734
申请日：2006-06-15
申请人： Douglas J. Dollinger , Marvin H. Caruthers , Jason R. Betley
发明人： Douglas J. Dollinger , Marvin H. Caruthers , Jason R. Betley
IPC分类号： C07H19/10 , C07H19/20 , C07H21/00
CPC分类号： C07H19/10 , C07B2200/11 , C07H19/20 , C07H21/00 , C07H21/04 , C40B40/06 , C40B50/14 , Y02P20/55
摘要： The invention provides methods for synthesizing oligonucleotides using nucleoside monomers having carbonate protected hydroxyl groups that are deprotected with α-effect nucleophiles. The α-effect nucleophile irreversibly cleave the carbonate protecting groups while simultaneously oxidizing the internucleotide phosphite triester linkage to a phosphodiester linkage. The procedure may be carried out in aqueous solution at neutral to mildly basic pH. The method eliminates the need for separate deprotection and oxidation steps, and, since the use of acid to remove protecting groups is unnecessary, acid-induced depurination is avoided. Fluorescent or other readily detectable carbonate protecting groups can be used, enabling monitoring of individual reaction steps during oligonucleotide synthesis. The invention is particularly useful in the highly parallel, microscale synthesis of oligonucleotides.
摘要翻译：本发明提供了使用具有碳酸酯保护的羟基的核苷单体合成寡核苷酸的方法，所述羟基被α-效应亲核试剂去保护。 α-效应亲核试剂不可逆地切割碳酸酯保护基团，同时将磷酸核苷酸亚磷酸三酯键与磷酸二酯键连接。该方法可以在中性至弱碱性pH的水溶液中进行。该方法不需要单独的脱保护和氧化步骤，并且由于不需要使用酸去除保护基团，所以避免了酸诱导的去血。可以使用荧光或其它容易检测的碳酸酯保护基团，使得能够监测寡核苷酸合成期间的各个反应步骤。本发明在寡核苷酸的高度平行，微尺度合成中特别有用。

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