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1. 发明申请

WO2002079126A1 CROSS-METATHESIS REACTION OF FUNCTIONALIZED AND SUBSTITUTED OLEFINS USING GROUP 8 TRANSITION METAL CARBENE COMPLEXES AS METATHESIS CATALYSTS 审中-公开
标题翻译：使用第8组过渡金属碳复合物作为元素催化剂的官能化和取代的烯烃的跨金属反应
公开(公告)号：WO2002079126A1
公开(公告)日：2002-10-10
申请号：PCT/US2002/010196
申请日：2002-04-01
申请人： CALIFORNIA INSTITUTE OF TECHNOLOGY , GRUBBS, Robert, H. , CHATTERJEE, Arnab, K. , CHOI, Tae-Lim , GOLDBERG, Steven, D. , LOVE, Jennifer, A. , MORGAN, John, P. , SANDERS, Daniel, P. , SCHOLL, Matthias , TOSTE, F., Dean , TRNKA, Tina, M.
发明人： GRUBBS, Robert, H. , CHATTERJEE, Arnab, K. , CHOI, Tae-Lim , GOLDBERG, Steven, D. , LOVE, Jennifer, A. , MORGAN, John, P. , SANDERS, Daniel, P. , SCHOLL, Matthias , TOSTE, F., Dean , TRNKA, Tina, M.
IPC分类号： C07C6/02
CPC分类号： C07F9/40 , C07C6/04 , C07C17/275 , C07C29/40 , C07C29/46 , C07C41/14 , C07C45/69 , C07C67/293 , C07C67/297 , C07C67/343 , C07C67/475 , C07C201/12 , C07C319/20 , C07C2531/22 , C07C2601/14 , C07C2601/16 , C07C2603/74 , C07D263/14 , C07D317/12 , C07D317/20 , C07D317/24 , C07F7/1892 , C07F9/4015 , C07F15/0046 , C07C25/13 , C07C47/21 , C07C69/007 , C07C69/78 , C07C69/732 , C07C69/56 , C07C321/14 , C07C69/16 , C07C69/533 , C07C69/145 , C07C69/157 , C07C69/18 , C07C205/06 , C07C33/483
摘要： The invention pertains to the use of Group 8 transition metal carbene complexes as catalysts for olefin cross-metathesis reactions. In particular, ruthenium and osmium alkylidene complexes substituted with an N-heterocyclic carbene ligand are used to catalyze cross-metathesis reactions to provide a variety of substituted and functionalized olefins, including phosphonate-substituted olefins, directly halogenated olefins, 1,1,2-trisubstituted olefins, and quaternary allylic olefins. The invention further provides a method for creating functional diversity using the aforementioned complexes to catalyze cross-metathesis reactions of a first olefinic reactant, which mayor may not be substituted with a functional group, with each of a plurality of different olefinic reactants, which may or may not be substituted with functional groups, to give a plurality of structurally distinct olefinic products. The methodology of the invention is also useful in facilitating the stereoselective synthesis of 1,2-disubstituted olefins in the cis configuration.
摘要翻译：本发明涉及第8族过渡金属卡宾配合物用作烯烃交叉复分解反应的催化剂。特别地，用N-杂环卡宾配体取代的钌和锇亚烷基配合物用于催化交叉复分解反应以提供各种取代和官能化的烯烃，包括膦酸酯取代的烯烃，直接卤代烯烃，三取代烯烃和季烯丙烯烯烃。本发明还提供了一种使用上述配合物来催化第一种烯属反应物（其可能不被官能团取代）的交叉复分解反应与多种不同的烯属反应物中的每一种的交叉复分解反应的方法，其可以或可能不被官能团取代，得到多个结构不同的烯属产物。本发明的方法还可用于促进顺式构型中1,2-二取代的烯烃的立体选择性合成。

2. 发明申请

WO2002079127A1 SELECTIVE RING-OPENING CROSS-METATHESIS OF CYCLOOLEFINS 审中-公开
标题翻译：选择性环开环交联蛋白
公开(公告)号：WO2002079127A1
公开(公告)日：2002-10-10
申请号：PCT/US2002/010395
申请日：2002-04-01
申请人： CALIFORNIA INSTITUTE OF TECHNOLOGY , MORGAN, John, P. , MORRILL, Christie , GRUBBS, Robert, H. , CHOI, Tae-Lim
发明人： MORGAN, John, P. , MORRILL, Christie , GRUBBS, Robert, H. , CHOI, Tae-Lim
IPC分类号： C07C6/02
CPC分类号： C07C67/343 , B01J31/18 , B01J31/2226 , B01J31/2273 , B01J31/24 , B01J31/2404 , B01J2231/543 , B01J2531/80 , B01J2531/821 , B01J2540/32 , C07C6/06 , C07C45/68 , C07C51/353 , C07C67/475 , C07C2531/22 , C07C47/21 , C07C49/203 , C07C57/13 , C07C69/587 , C07C69/757 , C07C69/74 , C07C69/602
摘要： A catalytic method is provided for a ring-opening cross-metathesis reaction between a cycloolefinic substrate and a second olefinic reactant, wherein the catalyst used is a transition metal alkylidene complex substituted with an N-heterocyclic carbene ligand. The substrates are selected so that the rate of the cross-metathesis reaction of the second olefinic reactant, k CM , is greater than or equal to the rate of the ring-opening metathesis reaction, k Ro . In this way, the predominant ROCM product is a monomer, dimer, and/or oligomer, but not a polymer. The invention additionally provides for selective production of an end-differentiated olefinic product, using trisubstituted cycloolefins as substrates and/or a subsequent cross-metathesis reaction following an initial ROCM step. The cycloolefinic substrates include low-strain olefins such as cyclohexene as well as higher strain olefins such as cyclooctene.
摘要翻译：提供了一种用于环烯基底物和第二烯属反应物之间的开环交叉复分解反应的催化方法，其中使用的催化剂是被N-杂环卡宾配体取代的过渡金属亚烷基络合物。选择底物使得第二烯属反应物的交叉复分解反应速率kCM大于或等于开环复分解反应速率kRo。以这种方式，主要的ROCM产物是单体，二聚体和/或低聚物，但不是聚合物。本发明另外提供了在初始ROCM步骤之后使用三取代的环烯烃作为底物和/或随后的交叉复分解反应来选择性生产末端分解的烯烃产物。环烯烃底物包括低应变烯烃如环己烯以及较高级烯烃如环辛烯。

3. 发明申请

WO2003070779A1 RING EXPANSION OF CYCLIC-OLEFINS BY OLEFIN METATHESIS REACTIONS WITH AN ACYCLIC DIENE 审中-公开
标题翻译：用烯丙基异构体反应与环状二烯的环烯烃的环扩展
公开(公告)号：WO2003070779A1
公开(公告)日：2003-08-28
申请号：PCT/US2003/005207
申请日：2003-02-19
申请人： CALIFORNIA INSTITUTE OF TECHNOLOGY
发明人： CHOI, Tae-Lim , LEE, Choon, Woo , RUTENBERG, Isaac, M. , KIM, Hyunjin, M. , GRUBBS, Robert, H.
IPC分类号： C08F4/80
CPC分类号： C07F7/1892 , B01J31/2265 , C08G61/08
摘要： This invention relates generally to synthetic procedures that include the step of ringopening metathesis of cyclic olefins and reaction with an acyclic diene co-reactant to produce olefin macrocycles by ring expansion, or alternatively, to produce regularly repeating A,B-alternating olefin polymers. The ring expansion of the cyclic olefin is provided by three types of sequential olefin metathesis (ring-opening, cross, and ring-closing olefin metathesis), and the A,B-alternating polymers are produced by simply varying the reaction conditions and/or reactant proportions and using only two types of olefin metathesis (ring-opening and cross) to provide regularly repeating ABAB...etc. polymers via ring-opening metathesis polymerization (ROMP). More particularly, the invention pertains to synthesis of olefin macrocycles and A,B-alternating olefin polymers via olefin metathesis reactions using a Group 8 transition metal complex as the metathesis catalyst. Macrocycles provided herein have a variety of uses in the pharmaceutical, biomedical, organic synthesis and chemical industries, such as the production of crown ethers that are useful as metal complexing species. Also, the polymers provided herein have utility in a variety of fields, including not only polymer chemistry per se, but also in the pharmaceutical, biomedical, and packaging industries where the structure and properties of polymers need to be tightly controlled.
摘要翻译：本发明一般涉及合成方法，其包括环状烯烃的环化复分解步骤和与无环二烯共反应物反应以通过环扩展产生烯烃大环化合物的步骤，或者替代地制备规则重复的A，B-交替烯烃聚合物。环烯烃的环扩展由三种顺序烯烃复分解（开环，交叉和闭环烯烃复分解）提供，而A，B交替聚合物是通过简单地改变反应条件和/或反应物比例，仅使用两种类型的烯烃复分解（开环和交叉）来提供定期重复的ABAB等。聚合物通过开环易位聚合（ROMP）。更具体地说，本发明涉及通过使用第8族过渡金属络合物作为复分解催化剂的烯烃复分解反应合成烯烃大环化合物和A，B-交替烯烃聚合物。本文提供的大环在药物，生物医学，有机合成和化学工业中具有多种用途，例如可用作金属络合物质的冠醚的生产。此外，本文提供的聚合物在各种领域中具有实用性，不仅包括聚合物化学本身，还包括在聚合物的结构和性质需要被严格控制的药物，生物医学和包装工业中。

4. 发明公开

EP1483300A1 RING EXPANSION OF CYCLIC-OLEFINS BY OLEFIN METATHESIS REACTIONS WITH AN ACYCLIC DIENE 审中-公开
标题翻译：作者环状烯烃通过与无环DIEN烯烃易位反应扩环
公开(公告)号：EP1483300A1
公开(公告)日：2004-12-08
申请号：EP03742846.3
申请日：2003-02-19
申请人： CALIFORNIA INSTITUTE OF TECHNOLOGY
发明人： CHOI, Tae-Lim , LEE, Choon, Woo , RUTENBERG, Isaac M. , GRUBBS, Robert, H.
IPC分类号： C08F4/80 , C08F32/04 , C07F17/02 , C07F15/02 , B01J21/08
CPC分类号： C07F7/1892 , B01J31/2265 , C08G61/08
摘要： This invention relates generally to synthetic procedures that include the step of ringopening metathesis of cyclic olefins and reaction with an acyclic diene co-reactant to produce olefin macrocycles by ring expansion, or alternatively, to produce regularly repeating A,B-alternating olefin polymers. The ring expansion of the cyclic olefin is provided by three types of sequential olefin metathesis (ring-opening, cross, and ring-closing olefin metathesis), and the A,B-alternating polymers are produced by simply varying the reaction conditions and/or reactant proportions and using only two types of olefin metathesis (ring-opening and cross) to provide regularly repeating ABAB...etc. polymers via ring-opening metathesis polymerization (ROMP). More particularly, the invention pertains to synthesis of olefin macrocycles and A,B-alternating olefin polymers via olefin metathesis reactions using a Group 8 transition metal complex as the metathesis catalyst. Macrocycles provided herein have a variety of uses in the pharmaceutical, biomedical, organic synthesis and chemical industries, such as the production of crown ethers that are useful as metal complexing species. Also, the polymers provided herein have utility in a variety of fields, including not only polymer chemistry per se, but also in the pharmaceutical, biomedical, and packaging industries where the structure and properties of polymers need to be tightly controlled.

5. 发明公开

EP1301458A1 SYNTHESIS OF FUNCTIONALIZED AND UNFUNCTIONALIZED OLEFINS VIA CROSS AND RING-CLOSING METATHESIS 有权
标题翻译：合成及上未官能官能化的烯烃通过交叉和闭环置换
公开(公告)号：EP1301458A1
公开(公告)日：2003-04-16
申请号：EP01950437.2
申请日：2001-06-25
申请人： CALIFORNIA INSTITUTE OF TECHNOLOGY
发明人： GRUBBS, Robert, H. , CHATTERJEE, Arnab, K. , MORGAN, John, P. , SCHOLL, Matthias , CHOI, Tae-Lim
IPC分类号： C07C67/02 , C07C317/14 , C07C233/09 , C07C205/06 , C07C61/35 , C07D323/02 , C07D263/04 , C07D303/04 , C07D309/16 , C07D309/18 , C07F7/04 , C07F9/28 , C07F15/00
CPC分类号： C07D303/22 , C07B37/00 , C07C45/673 , C07C45/69 , C07C45/72 , C07C67/293 , C07C67/343 , C07C201/12 , C07C231/12 , C07C259/06 , C07C315/04 , C07D263/22 , C07D263/24 , C07D309/12 , C07D309/30 , C07D315/00 , C07D317/12 , C07D319/12 , C07D319/14 , C07D321/08 , C07D413/12 , C07C49/597 , C07C317/14 , C07C233/09 , C07C233/11 , C07C205/06 , C07C205/56
摘要： The invention is directed to the cross-metathesis and ring-closing metathesis reactions between geminal disubstituted olefins and terminal olefins, wherein the reaction employs a Ruthenium or Osmium metal carbene complex. Specifically, the invention relates to the synthesis of α-functionalized or unfunctionalized olefins via intermolecular cross-metathesis and intramolecular ring-closing metathesis using a ruthenium alkylidene complex. The catalysts preferably used in the invention are of general formula (I) or (II), wherein: M is ruthenium or osmium; X and X1 are each independently an anionic ligand; L is a neutral electron donor ligand; and, R, R?1, R6, R7, R8, and R9¿ are each independently hydrogen or a substituent selected from the group consisting of C¿1?-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C2-C20 alkoxycarbonyl, C1-C20 alkylthio, C1-C20 alkylsulfonyl and C1-C20 alkylsulfinyl.

7. 发明公开

EP1379485A1 SELECTIVE RING-OPENING CROSS-METATHESIS OF CYCLOOLEFINS 审中-公开
标题翻译：环烯烃开环选择性交叉复分解
公开(公告)号：EP1379485A1
公开(公告)日：2004-01-14
申请号：EP02728658.2
申请日：2002-04-01
申请人： California Institute of Technology
发明人： MORGAN, John, P. , MORRILL, Christie , GRUBBS, Robert, H. , CHOI, Tae-Lim
IPC分类号： C07C6/02 , C07C6/04 , C07C6/06
CPC分类号： C07C67/343 , B01J31/18 , B01J31/2226 , B01J31/2273 , B01J31/24 , B01J31/2404 , B01J2231/543 , B01J2531/80 , B01J2531/821 , B01J2540/32 , C07C6/06 , C07C45/68 , C07C51/353 , C07C67/475 , C07C2531/22 , C07C47/21 , C07C49/203 , C07C57/13 , C07C69/587 , C07C69/757 , C07C69/74 , C07C69/602
摘要： A catalytic method is provided for a ring-opening cross-metathesis reaction between a cycloolefinic substrate and a second olefinic reactant, wherein the catalyst used is a transition metal alkylidene complex substituted with an N-heterocyclic carbene ligand. The substrates are selected so that the rate of the cross-metathesis reaction of the second olefinic reactant, kCM, is greater than or equal to the rate of the ring-opening metathesis reaction, kRo. In this way, the predominant ROCM product is a monomer, dimer, and/or oligomer, but not a polymer. The invention additionally provides for selective production of an end-differentiated olefinic product, using trisubstituted cycloolefins as substrates and/or a subsequent cross-metathesis reaction following an initial ROCM step. The cycloolefinic substrates include low-strain olefins such as cyclohexene as well as higher strain olefins such as cyclooctene.

8. 发明公开

EP1373170A1 CROSS-METATHESIS REACTION OF FUNCTIONALIZED AND SUBSTITUTED OLEFINS USING GROUP 8 TRANSITION METAL CARBENE COMPLEXES AS METATHESIS CATALYSTS 无效
标题翻译：功能化的交叉复分解和取代烯烃使用过渡金属集团8 CARBEN复杂的AS METHATESE催化剂
公开(公告)号：EP1373170A1
公开(公告)日：2004-01-02
申请号：EP02731215.6
申请日：2002-04-01
申请人： California Institute of Technology
发明人： GRUBBS, Robert, H. , CHATTERJEE, Arnab, K. , CHOI, Tae-Lim , GOLDBERG, Steven, D. , LOVE, Jennifer, A. , MORGAN, John, P. , SANDERS, Daniel, P. , SCHOLL, Matthias , TOSTE, F., Dean , TRNKA, Tina, M.
IPC分类号： C07C6/02 , C07C6/04 , C07C6/06
CPC分类号： C07F9/40 , C07C6/04 , C07C17/275 , C07C29/40 , C07C29/46 , C07C41/14 , C07C45/69 , C07C67/293 , C07C67/297 , C07C67/343 , C07C67/475 , C07C201/12 , C07C319/20 , C07C2531/22 , C07C2601/14 , C07C2601/16 , C07C2603/74 , C07D263/14 , C07D317/12 , C07D317/20 , C07D317/24 , C07F7/1892 , C07F9/4015 , C07F15/0046 , C07C25/13 , C07C47/21 , C07C69/007 , C07C69/78 , C07C69/732 , C07C69/56 , C07C321/14 , C07C69/16 , C07C69/533 , C07C69/145 , C07C69/157 , C07C69/18 , C07C205/06 , C07C33/483
摘要： The invention pertains to the use of Group 8 transition metal carbene complexes as catalysts for olefin cross-metathesis reactions. In particular, ruthenium and osmium alkylidene complexes substituted with an N-heterocyclic carbene ligand are used to catalyze cross-metathesis reactions to provide a variety of substituted and functionalized olefins, including phosphonate-substituted olefins, directly halogenated olefins, 1,1,2-trisubstituted olefins, and quaternary allylic olefins. The invention further provides a method for creating functional diversity using the aforementioned complexes to catalyze cross-metathesis reactions of a first olefinic reactant, which mayor may not be substituted with a functional group, with each of a plurality of different olefinic reactants, which may or may not be substituted with functional groups, to give a plurality of structurally distinct olefinic products. The methodology of the invention is also useful in facilitating the stereoselective synthesis of 1,2-disubstituted olefins in the cis configuration.

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