公开(公告)号：US06794534B2

公开(公告)日：2004-09-21

申请号：US09891144

申请日：2001-06-25

申请人： Robert H. Grubbs ,  Arnab K. Chatterjee ,  John P. Morgan ,  Matthias Scholl ,  Tae-Lim Choi

发明人： Robert H. Grubbs ,  Arnab K. Chatterjee ,  John P. Morgan ,  Matthias Scholl ,  Tae-Lim Choi

IPC分类号： C07C6952

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 &agr;-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 the general formula wherein: M is ruthenium or osmium; X and X1 are each independently an anionic ligand; L is a neutral electron donor ligand; and, R, R1R6, R7, R8, and R9 are each independently hydrogen or a substituent selected from the group consisting of C1-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.

摘要翻译： 本发明涉及孪生二取代的烯烃和末端烯烃之间的交叉复分解和闭环复分解反应，其中该反应采用钌或锇金属卡宾络合物。 具体地，本发明涉及通过分子间交叉复分解和使用亚烷基钌络合物的分子内闭合复分解来合成α-官能化或未官能化的烯烃。 本发明优选使用的催化剂是通式为：M为钌或锇; X和X 1各自独立地为阴离子配体; L为中性给电子体配位体; 并且R 1，R 1，R 6，R 7，R 8和R 9各自独立地为氢或选自C 1 -C 20烷基，C 2 -C 20烯基 ，C 2 -C 20炔基，芳基，C 1 -C 20羧酸酯，C 1 -C 20烷氧基，C 2 -C 20链烯氧基，C 2 -C 20炔氧基，芳氧基，C 2 -C 20烷氧基羰基，C 1 -C 20烷硫基，C 1 -C 20烷基磺酰基和C 1 -C 20烷基亚磺酰基。

公开(公告)号：US20070155975A1

公开(公告)日：2007-07-05

申请号：US11559399

申请日：2006-11-13

申请人： Robert Grubbs ,  Arnab Chatterjee ,  Tae-Lim Choi ,  Steven Godberg ,  Jennifer Love ,  John Morgan ,  Daniel Sanders ,  Matthias Scholl ,  F. Toste ,  Tina Trnka

发明人： Robert Grubbs ,  Arnab Chatterjee ,  Tae-Lim Choi ,  Steven Godberg ,  Jennifer Love ,  John Morgan ,  Daniel Sanders ,  Matthias Scholl ,  F. Toste ,  Tina Trnka

IPC分类号： C07F9/02 ,  C07F5/02 ,  C07F7/00 ,  C07C31/34 ,  C07C205/02 ,  C07C319/02

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 may or 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族过渡金属卡宾络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可能或可能不被官能团取代的第一种烯属反应物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， 或可以不被官能团取代，得到多个结构不同的烯烃产物。 本发明的方法还可用于促进顺式构型中的1,2-二取代烯烃的立体选择性合成。

公开(公告)号：US08846939B2

公开(公告)日：2014-09-30

申请号：US13494708

申请日：2012-06-12

申请人： Robert H. Grubbs ,  Matthias Scholl

发明人： Robert H. Grubbs ,  Matthias Scholl

IPC分类号： C07F15/00

CPC分类号： C07F15/0046 ,  B01J31/2273 ,  B01J31/2278 ,  B01J31/2295 ,  B01J2231/543 ,  B01J2531/821 ,  B01J2531/825 ,  C08G61/08

摘要： The present invention relates to novel metathesis catalysts with an imidazolidine-based ligand and to methods for making and using the same. The inventive catalysts are wherein: M is ruthenium or osmium; X and X1 are each independently an anionic ligand; L is a neutral electron donor ligand; and, R, R1 R6, R7, R8, and R9 are each independently hydrogen or a substituent selected for the group consisting of C1 C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, aryl, C1-C20 alkoxycarbonyl, C1-C20 alkyithiol, aryl thiol, C1-C20 alkylsulfortyl and C1-C20 alkylsulfinyl, the substituent optionally substituted with one or more moieties selected from the group consisting of C1-C20 alkyl, C1-C10 alkoxy, aryl, and a functional group. The inclusion of an imidazolidine ligand to the previously described ruthenium or osmium catalysts has been found to dramatically improve the properties of these complexes.

摘要翻译： 本发明涉及具有咪唑烷类配体的新型复分解催化剂及其制备和使用方法。 本发明的催化剂是其中：M是钌或锇; X和X1各自独立地为阴离子配体; L是中性电子给体配体; 并且，R 1，R 1，R 6，R 7，R 8和R 9各自独立地为氢或选自由C 1 -C 20烷基，C 2 -C 20烯基，C 2 -C 20炔基，芳基，C 1 -C 20烷氧基羰基，C 1 -C 20 烷基硫醇，芳基硫醇，C 1 -C 20烷基磺酰基和C 1 -C 20烷基亚磺酰基，所述取代基任选被一个或多个选自C 1 -C 20烷基，C 1 -C 10烷氧基，芳基和官能团的部分取代。 已经发现将咪唑烷配体包含在前述的钌或锇催化剂中可显着地改善这些络合物的性质。

公开(公告)号：US07329758B1

公开(公告)日：2008-02-12

申请号：US09576370

申请日：2000-05-22

申请人： Robert H. Grubbs ,  Matthias Scholl

发明人： Robert H. Grubbs ,  Matthias Scholl

IPC分类号： C07F15/00 ,  C07F7/02 ,  C08F4/80

CPC分类号： C07F15/0046 ,  B01J31/2273 ,  B01J31/2278 ,  B01J31/2295 ,  B01J2231/543 ,  B01J2531/821 ,  B01J2531/825 ,  C08G61/08

摘要： The present invention relates to novel metathesis catalysts with an imidazolidine-based ligand and to methods for making and using the same. The inventive catalysts are of the formula wherein: M is ruthenium or osmium; X and X1 are each independently an anionic ligand; L is a neutral electron donor ligand; and, R, R1 R6, R7, R8, and R9 are each independently hydrogen or a substituent selected from the group consisting of C1-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 alkylthiol, aryl thiol, C1-C20 alkylsulfonyl and C1-C20 alkylsulfinyl, the substituent optionally substituted with one or more moieties selected from the group consisting of C1-C10 alkyl, C1-C10 alkoxy, aryl, and a functional group selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen. The inclusion of an imidazolidine ligand to the previously described ruthenium or osmium catalysts has been found to dramatically improve the properties of these complexes. The inventive catalysts maintains the functional group tolerance of previously described ruthenium complexes while having enhanced metathesis activity that compares favorably to prior art tungsten and molybdenum systems.