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    IMIDAZOLIDINE-BASED METAL CARBENE METATHESIS CATALYSTS
    1.
    发明申请
    IMIDAZOLIDINE-BASED METAL CARBENE METATHESIS CATALYSTS 审中-公开

    公开(公告)号：US20160237101A9

    公开(公告)日：2016-08-18

    申请号：US14461180

    申请日：2014-08-15

    申请人： CALIFORNIA INSTITUTE OF TECHNOLOGY

    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 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 C2-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.

    IMIDAZOLIDINE-BASED METAL CARBENE METATHESIS CATALYSTS
    2.
    发明申请
    IMIDAZOLIDINE-BASED METAL CARBENE METATHESIS CATALYSTS 审中-公开
    基于咪唑烷的金属碳元素催化剂

    公开(公告)号：US20150038724A1

    公开(公告)日：2015-02-05

    申请号：US14461180

    申请日：2014-08-15

    申请人： CALIFORNIA INSTITUTE OF TECHNOLOGY

    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 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 C2-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.

    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。 本发明的催化剂具有下式：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 2，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烷基硫醇，芳基硫醇，C 1 -C 20烷基磺酰基和C 2 -C 20烷基亚磺酰基，任选被一个或多个选自 由C 1 -C 10烷基，C 1 -C 10烷氧基，芳基和选自羟基，硫醇，硫醚，酮，醛，酯，醚，胺，亚胺，酰胺，硝基，羧酸的官能团组成的组 ，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。 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。 本发明的催化剂保持了先前描述的钌络合物的官能团耐受性，同时具有与现有技术的钨和钼体系相比有利的增强的复分解活性。