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    • 4. 发明申请
    • HEXACOORDINATED RUTHENIUM OR OSMIUM METAL CARBENE METATHESIS CATALYSTS
    • 异丁烯酸丁酯或奥氏体金属碳酸盐METATHESIS催化剂
    • WO2003011455A1
    • 2003-02-13
    • PCT/US2002/019167
    • 2002-06-14
    • CALIFORNIA INSTITUTE OF TECHNOLOGY
    • GRUBBS, Robert, H.SANFORD, Melanie, S.MOORE, Jason, L.LOVE, Jennifer, A.TRNKA, Tina, M.
    • B01J31/00
    • C07C6/04B01J23/462B01J23/466B01J31/181B01J31/1815B01J31/183B01J31/2273B01J31/28B01J2231/543B01J2531/821B01J2531/825C07C6/06C07C2531/22C07F15/002C07F15/0046C08G61/06
    • 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 XI are the same or different and are each independently an anionic ligand; L, L 1' and L 2 are the same or different and are each independently a neutral electron donor ligand; and, R and R 1 are each independently hydrogen or a substituent selected from the group consisting of C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, aryloxy, C 2 -C¿20 ? alkoxycarbonyl, C 1 -C 20 alkylthio, C 1 -C 20 alkylsulfonyl and C 1 -C 20 alkylsulfinyl and silyl. Optionally, each of the R or R 1 substituent group may be substituted with one or more moieties selected from the group consisting of C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and aryl which in turn may each be further substituted with one or more groups selected from a halogen, a C 1 -C 5 alkyl, C 1 -C 5 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, L l' and L 2 is an N-heterocyclic carbene ligand.
    • 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。 本发明的催化剂具有下式:其中:M是钌或锇; X和XI相同或不同,各自独立地为阴离子配体; L,L 1和L 2相同或不同,各自独立地为中性给电子体配体; 和R 1和R 2各自独立地是氢或选自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 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C 1 -C 10烷基,C 1 -C 10烷氧基和芳基的部分取代,所述基团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。