公开(公告)号：US06818586B2

公开(公告)日：2004-11-16

申请号：US10172765

申请日：2002-06-14

申请人： Robert H. Grubbs ,  Melanie S. Sanford ,  Jason L. Moore ,  Jennifer A. Love ,  Tina M. Trnka

发明人： Robert H. Grubbs ,  Melanie S. Sanford ,  Jason L. Moore ,  Jennifer A. Love ,  Tina M. Trnka

IPC分类号： B01J3100

CPC分类号： C07C6/04 ,  B01J23/462 ,  B01J23/466 ,  B01J31/181 ,  B01J31/1815 ,  B01J31/182 ,  B01J31/1825 ,  B01J31/183 ,  B01J31/2273 ,  B01J31/28 ,  B01J2231/14 ,  B01J2231/543 ,  B01J2531/821 ,  B01J2531/825 ,  C07C6/06 ,  C07C2531/22 ,  C07F15/002 ,  C07F15/0046 ,  C08G61/06

摘要： The present invention relates to novel hexacoordinated metathesis catalysts 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 the same or different and are each independently an anionic ligand; L, L1′ and L2 are the same or different and are each independently a neutral electron donor ligand; and, R and R1 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 and silyl. Optionally, each of the R or R1 substituent group may be substituted with one or more moieties selected from the group consisting of C1-C10 alkyl, C1-C10 alkoxy, and aryl which in turn may each be further substituted with one or more groups selected from a halogen, a C1-C5 alkyl, C1-C5 alkoxy, and phenyl. Moreover, any of the catalyst ligands may further include one or more functional groups. Examples of suitable functional groups include but are not limited to: hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, halogen, alcohol, sulfonic acid, phosphine, imide, acetal, ketal, boronate, cyano, cyanohydrin, hydrazine, enamine, sulfone, sulfide, and sulfenyl. In certain embodiments, at least one of L, L1′ and L2 is an N-heterocyclic carbene ligand.

摘要翻译： 本发明涉及新型六配位复分解催化剂及其制备和使用方法。 本发明的催化剂为糠醛：M是钌或锇; X和X 1相同或不同，各自独立地为阴离子配位体; L，L 1和L 2相同或不同 并且各自独立地为中性电子给体配体; 和R 1和R 2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， C20链烯氧基，C2-C20炔氧基，芳氧基，C2-C20烷氧基羰基，C1-C20烷硫基，C1-C20烷基磺酰基和C1-C20烷基亚磺酰基和甲硅烷基。 任选地，R或R ​​1取代基中的每一个可以被一个或多个选自以下的部分取代：C 1 -C 10烷基，C 1 -C 10烷氧基和芳基，其又可以进一步被一个或多个 更多选自卤素，C 1 -C 5烷基，C 1 -C 5烷氧基和苯基的基团。 此外，任何催化剂配体还可以包括一个或多个官能团。 合适的官能团的实例包括但不限于：羟基，硫醇，硫醚，酮，醛，酯，醚，胺，亚胺，酰胺，硝基，羧酸，二硫化物，碳酸酯，异氰酸酯，碳二亚胺，碳烷氧基，氨基甲酸酯，卤素 醇，磺酸，膦，酰亚胺，缩醛，缩酮，硼酸酯，氰基，氰醇，肼，烯胺，砜，硫化物和亚磺酰基。 在某些实施方案中，L，L'和L 2中的至少一个是N-杂环卡宾配体。

公开(公告)号：US06759537B2

公开(公告)日：2004-07-06

申请号：US10017489

申请日：2001-12-14

申请人： Robert H. Grubbs ,  Jennifer A. Love ,  Melanie S. Sanford ,  Tina M. Trnka ,  Jason L. Moore

发明人： Robert H. Grubbs ,  Jennifer A. Love ,  Melanie S. Sanford ,  Tina M. Trnka ,  Jason L. Moore

IPC分类号： C07D22706

CPC分类号： C08G61/06 ,  B01J31/181 ,  B01J31/1815 ,  B01J31/182 ,  B01J31/1825 ,  B01J31/183 ,  B01J31/2273 ,  B01J2231/14 ,  B01J2231/543 ,  B01J2531/821 ,  B01J2531/825 ,  C07C6/04 ,  C07C6/06 ,  C07C2531/22 ,  C07F15/002 ,  C07F15/0046

摘要： The present invention relates to novel hexacoordinated metathesis catalysts 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 the same or different and are each independently an anionic ligand; L, L1′ and L2 are the same or different and are each independently a neutral electron donor ligand, wherein at least one L, L1′ and L2 is an N-heterocyclic carbene ligand; and, R and R1 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. Optionally, each of the R or R1 substituent group may be substituted with one or more moieties selected from the group consisting of C1-C10 alkyl, C1-C10 alkoxy, and aryl which in turn may each be further substituted with one or more groups selected from a halogen, a C1-C5 alkyl, C1-C5 alkoxy, and phenyl. Moreover, any of the catalyst ligands may further include one or more functional groups. Examples of suitable functional groups include but are not limited to: hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen.

摘要翻译： 本发明涉及新型六配位复分解催化剂及其制备和使用方法。 本发明的催化剂为糠醛：M是钌或锇; X和X 1相同或不同，各自独立地为阴离子配位体; L，L 1和L 2相同或不同 并且各自独立地为中性电子给体配体，其中至少一个L，L 1和L 2为N-杂环卡宾配体; 和R 1和R 2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， C20链烯氧基，C2-C20炔氧基，芳氧基，C2-C20烷氧基羰基，C1-C20烷硫基，C1-C20烷基磺酰基和C1-C20烷基亚磺酰基。 任选地，R或R ​​1取代基中的每一个可以被一个或多个选自以下的部分取代：C 1 -C 10烷基，C 1 -C 10烷氧基和芳基，其又可以进一步被一个或多个 更多选自卤素，C 1 -C 5烷基，C 1 -C 5烷氧基和苯基的基团。 此外，任何催化剂配体还可以包括一个或多个官能团。 合适的官能团的实例包括但不限于羟基，硫醇，硫醚，酮，醛，酯，醚，胺，亚胺，酰胺，硝基，羧酸，二硫化物，碳酸酯，异氰酸酯，碳二亚胺，碳烷氧基，氨基甲酸酯和 卤素。