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1.发明授权Tetra- and penta-o-benzyl-protected, C-4 activated-epicatechin and -catechin monomers and processes for their preparation and use 失效四 - 和五 - 邻 - 苄基保护的C-4活化表儿茶素和儿茶素单体及其制备和使用方法公开(公告)号：US07507831B2
公开(公告)日：2009-03-24
申请号：US11329467
申请日：2006-01-11
IPC分类号： C07D417/12 , C07D311/30
CPC分类号： C07D311/62 , C07D417/12 , C07D417/14
摘要： Various processes are disclosed for preparing protected epicatechin oligomers having (4β,8)-interflavan linkages. In one process, a tetra-O-protected epicatechin monomer or oligomer is coupled with a protected, C-4 activated epicatechin monomer in the presence of an acidic clay such as a mortmorillonite clay. In another process, a 5,7,3′,4′-benzyl protected or a 3 -acetyl-, 5,7,3′,4′-benzyl protected epicatechin or catechin monomer or oligomer is reacted with 3 -O-acetyl-4-[(2-benzothiazolyl)thio]-5,7,3′,4′-tetra-O-benzylepicatechin in the presence of silver tetrafluoroborate. In another process, two 5,7,3′,4′-benzyl protected epicatechin monomers activated with 2-(benzothiazolyl)thio groups at the C-4 positions are cross-coupled in the presence of silver tetrofluoroborate. A process is also disclosed for reacting an unprotected epicatechin or catechin monomer with 4-(benzylthio) epicatechin or catechin. The use of naturally-derived and synthetically-prepared procyanidin (4β,8)4-pentamers to treat cancer is also disclosed.
摘要翻译： 公开了用于制备具有（4beta，8） - 间连环的保护的表儿茶素低聚物的各种方法。 在一个方法中，四氧化物保护的表儿茶素单体或低聚物在保护的C-4活化的表儿茶素单体的存在下，在酸性粘土如失
桑土粘土的存在下偶合。 在另一种方法中，将5,7,3'，4'-苄基保护或3-乙酰基，5,7,3'，4'-苄基保护的表儿茶素或儿茶素单体或低聚物与3-O-乙酰基 -4 - [（2-苯并噻唑基）硫基] -5,7,3'，4'-四-O-苯甲酸酯在四氟硼酸银的存在下反应。 在另一种方法中，在C-4位上用2-（苯并噻唑基）硫基活化的两个5,7,3'，4'-苄基保护的表儿茶素单体在四氟硼酸银的存在下交联。 还公开了使未保护的表儿茶素或儿茶素单体与4-（苄硫基）表儿茶素或儿茶素反应的方法。 还公开了使用天然衍生的和合成制备的原花青素（4beta，8）4-五聚体来治疗癌症。-
2.发明授权Synthesis of epecatechin-4&agr;, 8-epicatechin dimers and derivatives thereof 失效表儿茶素-4α，8-表儿茶素二聚体及其衍生物的合成公开(公告)号：US06720432B2
公开(公告)日：2004-04-13
申请号：US10214830
申请日：2002-08-08
IPC分类号： C07D31500
CPC分类号： C07D311/74 , C07D311/62 , Y02P20/55
摘要： Oligomeric procyanidins containing 4&agr;-linked epicatechin units are rare in nature and have hitherto not been accessible through stereoselective synthesis. Provided herein is the preparation of the prototypical dimer, epicatechin-4&agr;,8-epicatechin, by reaction of the protected 4-ketones with aryllithium reagents derived by halogen/metal exchange from the aryl bromides. Removal of the 4-hydroxyl group from the resulting tertiary benzylic alcohols is effected by tri-n-butyltin hydride and trifluoroacetic acid in a completely stereoselective manner, resulting in hydride delivery exclusively from the &bgr; face.
摘要翻译： 含有4α-连接的表儿茶素单元的低聚原花青素在自然界中是罕见的，并且迄今尚未通过立体选择性合成进行。 本文提供了通过将受保护的4-酮与芳基溴化物的卤素/金属交换衍生的芳基锂试剂反应制备原型二聚体，表儿茶素-4α，8-表儿茶素。 从所得叔苄醇中除去4-羟基由三正丁基锡氢化物和三氟乙酸以完全立体选择的方式进行，从而产生仅从β面产生的氢化物。
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3.发明授权Synthesis of dimeric, trimeric, tetrameric pentameric, and higher oligomeric epicatechin-derived procyanidins having 4,8-interflavan linkages and their use to inhibit cancer cell growth through cell cycle arrest 失效二聚体，三聚体，四聚体五聚体和更高级低聚表儿茶素衍生的原花青素具有4,8-间氯联的合成及其通过细胞周期停滞抑制癌细胞生长的用途公开(公告)号：US07067679B2
公开(公告)日：2006-06-27
申请号：US10658241
申请日：2003-09-09
IPC分类号： C07D311/26
CPC分类号： C07D311/62 , C07D417/12 , C07D417/14
摘要： Various processes are disclosed for preparing protected epicatechin oligomers having (4β,8)-interflavan linkages. In one process, a tetra-O-protected epicatechin monomer or oligomer is coupled with a protected, C-4 activated epicatechin monomer in the presence of an acidic clay such as a mortmorillonite clay. In another process, a 5,7,3′,4′-benzyl protected or a 3-acetyl-, 5,7,3′,4′-benzyl protected epicatechin or catechin monomer or oligomer is reacted with 3-O-acetyl-4-[(2-benzothiazolyl)thio]-5,7,3′,4′-tetra-O-benzylepicatechin in the presence of silver tetrafluoroborate. In another process, two 5,7,3′,4′-benzyl protected epicatechin monomers activated with 2-(benzothiazolyl)thio groups at the C-4 positions are cross-coupled in the presence of silver tetrofluoroborate. A process is also disclosed for reacting an unprotected epicatechin or catechin monomer with 4-(benzylthio)epicatechin or catechin. The use of naturally-derived and synthetically-prepared procyanidin (4β,8)4-pentamers to treat cancer is also disclosed.
摘要翻译： 公开了用于制备具有（4beta，8） - 间连环的保护的表儿茶素低聚物的各种方法。 在一个方法中，四氧化物保护的表儿茶素单体或低聚物在保护的C-4活化的表儿茶素单体的存在下，在酸性粘土如失
桑土粘土的存在下偶合。 在另一种方法中，将5,7,3'，4'-苄基保护或3-乙酰基，5,7,3'，4'-苄基保护的表儿茶素或儿茶素单体或低聚物与3-O-乙酰基 -4 - [（2-苯并噻唑基）硫基] -5,7,3'，4'-四-O-苯甲酸酯在四氟硼酸银的存在下反应。 在另一种方法中，在C-4位上用2-（苯并噻唑基）硫基活化的两个5,7,3'，4'-苄基保护的表儿茶素单体在四氟硼酸银的存在下交联。 还公开了使未保护的表儿茶素或儿茶素单体与4-（苄硫基）表儿茶素或儿茶素反应的方法。 还公开了使用天然衍生的和合成制备的原花青素（4beta，8）4质子以治疗癌症。-
公开(公告)号：US06476241B1
公开(公告)日：2002-11-05
申请号：US09655360
申请日：2000-09-05
IPC分类号： C07D31158
CPC分类号： C07D311/74 , C07D311/62 , Y02P20/55
摘要： Oligomeric procyanidins containing 4&agr;-linked epicatechin units are rare in nature and have hitherto not been accessible through stereoselective synthesis. Provided herein is the preparation of the prototypical dimer, epicatechin-4&agr;,8-epicatechin, by reaction of the protected 4-ketones with aryllithium reagents derived by halogen/metal exchange from the aryl bromides. Removal of the 4-hydroxyl group from the resulting tertiary benzylic alcohols is effected by tri-n-butyltin hydride and trifluoroacetic acid in a completely stereoselective manner, resulting in hydride delivery exclusively from the &bgr; face.
摘要翻译： 含有4α-连接的表儿茶素单元的低聚原花青素在自然界中是罕见的，并且迄今尚未通过立体选择性合成进行。 本文提供了通过将受保护的4-酮与芳基溴化物的卤素/金属交换衍生的芳基锂试剂反应制备原型二聚体，表儿茶素-4α，8-表儿茶素。 从所得叔苄醇中除去4-羟基由三正丁基锡氢化物和三氟乙酸以完全立体选择的方式进行，从而产生仅从β面产生的氢化物。
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5.发明授权公开(公告)号：US07244855B2
公开(公告)日：2007-07-17
申请号：US10481729
申请日：2003-10-02
IPC分类号： C07D311/00
CPC分类号： C07D311/62 , C07D417/12 , C07D417/14
摘要： Various processes are disclosed for preparing procyanidin oligomers having (4,8)-interflavan linkages. In an improved process, a tetra-O-protected-epicatechin or -catechin monomer or oligomer is coupled with a protected, C-4 alkoxy-activated-epicatechin or -catechin monomer in the presence of an acidic clay instead of a Lewis acid. In a second process, a 5,7,3′,4′-tetra-O-protected or preferably penta-O-protected-epicatechin or -catechin monomer or oligomer is reacted with a tetra-O-protected or preferably penta-O-protected-epicatechin or -catechin monomer having a thio activating group at the C-4 position; the coupling is carried out in the presence of silver tetrafluoroborate. In third process, two molecules of a penta-O-protected-epicatechin or -catechin monomer activated with a 2-(benzothiazolyl)thio group at the C-4 position are self-condensed in the presence of silver tetrafluoroborate. An improved two-step process for preparing a C-4 alkoxy activated tetra-O-benzyl-protected, 8-bromo-blocked-epicatechin or -catechin monomer is also provided. The use of naturally-derived and synthetically-prepared procyanidin (4β,8)4-pentamers to treat cancer is also disclosed.
摘要翻译： 公开了用于制备具有（4,8） - 连续黄烷键的原花青素低聚物的各种方法。 在改进的方法中，在酸性粘土代替路易斯酸的情况下，将四-O-保护的表儿茶素或儿茶素单体或低聚物与受保护的C-4烷氧基 - 表儿茶素或儿茶素单体偶合。 在第二种方法中，5,7,3'，4'-四-O-保护的或优选五-O-保护的表儿茶素或儿茶素单体或低聚物与四-O-保护的或优选五-O 在C-4位具有硫代活化基团的保护表儿茶素或儿茶素单体; 在四氟硼酸银的存在下进行偶合。 在第三种方法中，在四氟硼酸银存在下，用2-（苯并噻唑基）硫基在C-4位上活化的五分子保护的表儿茶素或儿茶素单体的两分子是自缩合的。 还提供了一种用于制备C-4烷氧基活化的四-O-苄基保护的8-溴封闭的表儿茶素或儿茶素单体的改进的两步法。 还公开了使用天然衍生的和合成制备的原花青素（4beta，8）4质子以治疗癌症。
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6.发明授权Synthesis of epecatechin-4α, 8-epicatechin and -catechin dimers and derivatives thereof 失效表儿茶素-4α，8-表儿茶素和儿茶素二聚体及其衍生物的合成公开(公告)号：US07126014B2
公开(公告)日：2006-10-24
申请号：US10783801
申请日：2004-02-20
IPC分类号： C07C311/76
CPC分类号： C07D311/74 , C07D311/62 , Y02P20/55
摘要： Oligomeric procyanidins containing 4α-linked epicatechin units are rare in nature and have hitherto not been accessible through stereoselective synthesis. Provided herein is the preparation of the prototypical dimer, epicatechin-4α,8-epicatechin, by reaction of the protected 4-ketones with aryllithium reagents derived by halogen/metal exchange from the aryl bromides. Removal of the 4-hydroxyl group from the resulting tertiary benzylic alcohols is effected by tri-n-butyltin hydride and trifluoroacetic acid in a completely stereoselective manner, resulting in hydride delivery exclusively from the β face.
摘要翻译： 含有4α-连接的表儿茶素单元的低聚原花青素在自然界中是罕见的，并且迄今尚未通过立体选择性合成进行。 本文提供了通过将受保护的4-酮与芳基溴化物的卤素/金属交换衍生的芳基锂试剂反应制备原型二聚体，表儿茶素-4α，8-表儿茶素。 从所得叔苄醇中除去4-羟基由三正丁基锡氢化物和三氟乙酸以完全立体选择的方式进行，从而产生仅从β面产生的氢化物。
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公开(公告)号：US06271379B1
公开(公告)日：2001-08-07
申请号：US09520497
申请日：2000-03-08
IPC分类号： C07D22122
CPC分类号： C07D213/64 , C07D221/22
摘要： Intermediates useful for the synthesis of huperzine A represented by the structures below, and methods for their synthesis, wherein: R1 is lower alkyl, benzyl, or substituted benzyl; X is a suitable leaving group; Y is an electron withdrawing group that can subsequently be converted into an amino group; one broken line is present as a carbon—carbon bond and the other broken line is absent, where the broken line forms an unconjugated carbon—carbon double bond, which double bond may be endocyclic whereby n is 3 or the double bond may be exocyclic whereby n is 2.
摘要翻译： 用于合成由以下结构表示的石杉碱甲的中间体及其合成方法，其中：R1为低级烷基，苄基或取代的苄基; X为合适的离去基团; Y为可以随后为 转化为氨基;一条虚线以碳 - 碳键存在，另一条虚线不存在，其中虚线形成非共轭碳 - 碳双键，该双键可为内环，由此n为3或 双键可以是环外，其中n是2。
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